FUNDAMENTAL _UNIVE SITY PHYSICS

- VOLIJME'I1
-
ClUANTUM AND STATISTICAL PHYSICS

MARCELO ALONSO

Department of Scienli~ Affairs, Organization of American States

EDWARD J. FINN
Deparl1Mtll oj Phyaiu, GeorgeWwri Unirernty

Re.d ins, MaWlchus.cltS M. nlo I".,k, Californi a

ADDISON_WESLEY PUBLISHING COMPANY Don Mi lls. Oma';'" W"kingham. England . AmSlerdam. Bonn. SY~1\~Y
Singapore . Tokyo . Madrid . ikJgOI Santiago. San uan

 they may utilize Ihis knowledge in lIubsequent undergraduate COUI1lCIl. This procedure
is strongly endor!l('d by the Commission on College Physicil. Prescnt trends in biology
CONTENTS
and engineering demand that Students in these fields also have a basic understanding of
the IIOlid state and of moleeular litructure. Therefore we have been careful to introduce
thc student to quantum m{'(:hsnics in a ....ay wh ich, although elementary, allowil him to
apl)ly qualltum conccpU to diffcrent situations.
Chapur I is an introduction to the foundation of quantum idcas, This ia followed in
Chapter 2 by thc nCCC.l!!!ary background in qualltum mechanics; here we emphasise the
lIay ill which phy!!ical information about a system is extracted from the shape of the
potential-energy function and a kno .... ledge of the general natllre of .... ave function!!, In
the slIceee<iing chapters, 3 through 9, quantal concepLs snd tec hniques are applied to the
analysis of atom!!, molecules, IIOlids, nuclei, and fundamental particles.
In the second part of the text (designated Statistical Physics), we use statistical methods
10 consider the properties of matter in bulk . Li ke quan tum mechaniclI, statistical physics I'ART I QUANTUM PIIYSICS
is a .... ell-founded, powerful tool, to whic h the student should Ix- introduced as early &II
poS/!ible, After di&CUSlIing cla.ssical statistical mccha nics in Chapter 10, we present thermo- The Foundations of Qunntum Ph ysics
dYllamics fro m a statistical point of view in Chapter I I and apply it to both idea l and
t./ C h a ptc r 1
real gases in Chal)\er ] 2, We are firmly convinccd t hat this is the most al)propriate met hod 'I etic radiation 4 [I] Blackbody
to follow in in troducing the ~tudent to the concepts of thermodyna mics, The text ends Introduction 4 0 b eCir0'!lagn.. ] 1 0' Scatteri ng of rad iation
" 7 0 Pholocieclnc emlS/!IOIl , 22 0
with a brief introd uction to quantum statistic~ in Chapter 13. ra ' lallon Photons 18 0 Stationary ~tates,
by free electrons 14 0 . t 26 0 Interaction of
Since many students now Icaru the basic ideas of relativity in their general physica
course, the apecial theory of rclativity is discussed in the appendix. (A more complete
Ex..... rimental evidence of 8tat10nar~' 8ta
. "- . ' I t
ell,
29 0 Particles an Ie II
',d 33 0 Particles
radiation Wit I rna ~ - Heisenbcrg'~ uncertainty Pli.neiple f~r
d iscussion of rc lativity appeal1l in Volumes I and II of thc series.) Several collateral
and wave packets
position and momentum
0" 0 The uncertainty relation for time
lOllics, such all group velocity and thc met hods of particlc detection, are also discussed
in the appelldix. and energy 43
We have kellt the mathematical requiremenLs within the top ics covcred by a staudard
calculus COUI1Je, We have abo often cither omitted or relegated to the problem sections Chapter 2 Quantum Mech a ni cs
thOllC mathematical calculations which are not essential 10 an understauding of the main
. V ,{ l ion and Ilroba biJity density ~ 0
trend of physical idc&ll; one example of such calculations is the wmetimes boresome ta.sk
of linding certain Wluliolls to Schr&linger's cquation.
Introd~ctlo~ 53 O. ' &\ e un~)otential stell 59 0' Particle 111 &
Schr6!hngcr Bequallon 56 0 . .,' 7' 0 Energy levels
~Iany applications of the fundamental principles, II.S well as the di&Cussion of a few , bo 63 0 The harmomc OSCI ator " . 0
potential x . ' Potential barrier penelrattOn 8 0
more advanced tOpi cs, appear in the form of worked cxamples. The text ha.s been "'ritten and wave {uncllons 111 ~eneral 75 c;it 88 0 The timc-dependent
so that the student may omit all examples at hia lirst reading. During a second read ing Symmetry wave fUnctIOn s, and pa .
.'
r b b',"'Ag and selection
. 00 0 TranSit ion pro a I 1.1""
the student should consider thOl!e examples chosen by the instructor. The instructor may ~~~~ng~ t~~t}~~mal theory of quautum mechanics 96
diseuS/! these examplell at hill convenience or propose them on a selective basis. Certain
sectionll cf the text may be omitted without loss of continuity. The problema at the end
Chapte r 3 Atoms with One Elcctron
of eaeh ehaptcr follow the sequence of the chapter, with a fe"' more difficult problems at
the end. The large number of varied problems means that the instructor can chOOSe
. The hydrogen atom 109 0 T he spectrum of
problcms to mauh the abilities of his students. Hence by proper selection of the material
in this text, the instructor can adal)t the text to a one- or two-semester COllrse and a t t he
~n~~g~~tl~~5Ib ~uantiJalion of angular moment2", mO]]~~
y f . nder central forces 1
sa.me time give the studcnt both a challenge and a motivation to mect that challenge, One-electron wave UllctlonB u '135 0 Addition of angular
Zeeman effect 132 0 Eleetron spm ,
We want to exprcss our gra t itude to all those who, by the ir assistancc and encourage_ ~omcnta 137 0 Spin-orbit interaction 139
ment, havc made this work poS/!ible, We recognize in particular Professor David Lazarus,
whOl!e comments and criticisms helped to improve ma ny aspects of the text, Last-b ut Atoms wilh Man y Electrons
not least- we thank OlLr wives, who have 80 patieutly stood by us. )' Chapler 4.
. a""m
I trad uction ] 50 0 T he hehum 'A 150 0 The exclusiOll
L-S
Wa6AinglQlI, D. C,
i\Jarcclo Alonso n,. 58 0 Electronic structurc of atoms 161 0
January 1968 prmclple I .th one or tl"O valcnce elcctrons 171 0
Edward J . fo'inn coupling 164 0 Atoms WI
X-ray sf>eclra 176
~ii
 i.
riii

Chapter 5 Molcc ulu :\TBnv_partide ~rstems: heat 466 0 The fir.!~ law of th~rm~ynamics
467 i:J Grallhical repl'CS('ntation of prOCe"',"(" 469 0 SI)eCla ,
A_~ 473 0 Entropy and the !OeCond Ill"' of thcrmodYI,lalmes
Introduction 183 0 The hydrogen molecule ion 183 0 proc....,..,....
475 0 Entrop)' and heal 4SO 0 '" l _cU~lon ' ""f 11f()CeS'!eS III terms
:\Ioleeular orbitals of diatomic molecules 191 0 Electronic of entropy 484
configuration of some diatomic moleeules 194 0 Polyatomic
1Il0leeulC3 202 0 Conjugated molecules 208 0 i\lolecular
rotat ions 212 0 :\Iolecular \'ibrations 215 0 Electronic transitions Chupl"'r 12 Thermal l'rol""rl ics or Ga~..!I
in moleeulC3 222 0 Conclusion 225
Introduction 494 0 The equation of state of an id~al gas 4~4 0
Chapter 6 Solids Equation of state for real g!l.SCII 497 0 lIeat.capaclt y of BIl.ldeal
monatomic gail 504 0 lIeat capacities of (1.11 Ideal PQiyatomlc gB.'!
506 0 Thc principle of equipartition of energy 512
Introduction 231 0 Types of solids 231 0 Band theory of solids
243 0 Free-electron modcl of a solid 246 0 Electron motion in
a l>eriodic structure 251 0 Conductors, insulatoT$, and semiconductors Chapter 13 Quantu", S latis li c~
261 0 Quantum theory of electrical conductivity 268 0 Radiative
traMitions in solids 274 Introduction 519 0 Fermi- Dirac dill\rl~nti?n law ~l~ 0 The
, 2" 0 '\,',Ilication of Fermi-DIme statistICS to electrons
e1cc ron gas w ' , , ' \ 528 0 The photon
Chapter 7 N u c lear Str u cture , metals 526' 0 Bose-Einstein dl~tnbiitlon aw , '
~':.s 531 0 Heat capacity of solids 536 0 The ldenl gas m
Introduction 283 0 Isotopes, isotones, and isobars 283 0 The quantum 5tallstics 540
atomic mass unit 286 0' Properties of the nucleus 286 0 Nuclear
binding energy 2930 Nuclear forces 298 0 The ground stale of
the deuteron 301 0 Neutron-proton scattering at 10'" energies
303 0 The shell model 310 0 Nuclear radiative transitions 319 I Relativistic mechanics 55! 0 II Colli~ion8 555 0 '.11, G~ouP
,1 " '"" 0 IV Some u<cful integrals 562 0 V Stlrhngs
Chapter 8
\eoelY"",-, d 1'1' "'0
formula 563 0 VI l..agrange's undctermine mu II]) le\'!l .........
VI I The detection of parlicJCII 564
Introductioll 329 0 Radioactivedecay 329 0 Al pha decay
335 0 Bela decay 340 0 Nuclear reactions 348 0 Nuclear
fission 357 0 ~uc1ear fU.'lion 363 0 The origin of the elements 367 Tabl~ 577

Chapter 9 .'undamenta l Partie!es List or Tables 581

Introduction 377 0 Particle genealogy 378 0 Particles and Answers to Odd_Numbe red Problc ll ul :>83
antiparticles 379 0 Particle instability 386 0 The conservation
111."'.'1 397 0 Invariance, symmetry, and conservation laws 403 0 Ind ex 589
Resonances 414 0 What is a fundamental pMticle? 419

PART 2 STATISTICAL PIIYS ICS

Chapter 10 Clussiea l Statis ticatl\Teeh anies

Introd uction 434 Ql Statistical equilibrium 434 m The

Maxwell-Boltzmann distribution law 436 m Temperature 4~3 0
T hermal equilibrium 448 ta Application t.o the ideal gas 450

Chapter 11 Th er mod y n a mi cs

Introduction 462 0 Conservation of cnergy of a system of

particlCII 462 0 )lanY-)JarticJe systems: ",ork 464 0
 PART 1
QUANTUM PHYSICS

1 The Foundalions of Quanlum Physics

2 Quanlum NIechanics
3 Atoms wilh One Electron
I, Ato"", wilh Many Eleclrons
5 Molecules
6 Solids
7 Nuclear Slruclure
8 N uciear Processes
9 Fundamental Parlicles
, 1
One of the fundamental objectivC8 of physics is to analyze Ole proper~iCfl of th e
basic components of matter and the processes that occur among them as 8. result THE FOUNDATIONS OF
of their interactions. These basic components-called fundamental or elementary
particles-arc electrons, protOIlS, neutrons (and others) which group together to
foml nuclei, at.oms, and molecules. These groups, in tum, combine to form matter
QUANTUM PHYSICS
in bulk. Although the motion of fundamental particles complies with the prin.
ciples of conservation of momentum, angular momentum, and cllergy, the analy-
sis of this moLiOIl requires a framework different in several respects from the one
developed in classical (or Newtonian) mechanics for the analysis of macroscopic
motion. This more refined theory is called quantum mechania. We must under-
stand it well before we embark on a discussion of atoms, molecules, and nuclei.
Fortunately, atoms and molecules are essentially the result of eiectroma{I'lelic inler-
actiOIlS between the positively charged nuclei and the negatively charged eleetrons.
ThILS we can discuss atoms and molecules, without having to appeal to other IC$S-
well-understood forces, by combining the laws of electromagnetism with those of
quantum mechanics. The same technique may also be used for gases, liquids, and
solids. On tho other hand, nuclei aro basically the result of a new type of force, the
so-called s(rollO or nuc..Iear interaction. Since the strong interactiOll is not yet well
understood, its annlysis is much more involved . Consequently, in lhis text our
discussion of nuclei must be of a more descriptive nature. 1.1 Introduction
Perhaps the most dynamic and stimulating ficld of contemporary ])hysies is the 1.2 Electromagnetic Radiation
study of the fundamental particles. The interactions observed between theso par_
1.3 Blackbody Radiation
ticles require the introduction of another type of force, in addition to the strong
interaction. This force is called the weak irlleradion. Another force, the gr(U)ita- 1.4 Photoelectric Emission
lional interadu.m, which is the weakest of all interactions, plays a lesser role insofar 1.5 Scallering of Radiation by Free Electrons
as the basic structure of matter is concerned.
The relative value of the four interactions is: 1.6 Pholon1l
1.7 Stationary States
Strong
Electromagnetic 1O ~~ 1.8 Experimental Evidence of Stationary Slates
Weak IO ~13 1.9 I nleraclion of Radiation with Malter
Gravitational 1O- 3s 1.10 Particles and Fields
The procCSSC8 involving fundamentsl particles have motivated a new formalism, 1.11 Particles and Wave Packets
somewhat different from quantum mechanics, called quantum field theory. This 1.12 Heisenberg's Uncertainty Principle for
theory, however, is too complex to be considered in this text.
Position and Momentum
1.13 The Uncertainly Relation for Time and Energy
 , TM /owzdnIiotu 0/ quanlum phy.iQ
1.1 Introduction
By the end of the nineteenth century, and during the first qoortcr of the twen t ieth
experimental evidence began to accumulate which indicated that the interaction of
electromagnetic radia~i on with matter was not entirely in acco rdance with the Is
o,f electromagnetism. These laws were the result. of the work of Ampere, Laplace,
l'araday, Henry, J\laxwell, and many others, and arc sYllthesized in .Maxwell's
equations for the electromagnetic field. At. the same time the theory of the atomic
structure of matt-er was developing, mainly 9.8 8 result of the discovery of the elec-
tron ~nd the confinnation of the nuclear model of the atom. Still another series of
experiments forced the physicist to review his concepts of the motion of subatomic
particles, since they apparently did not move precisely in accordance with the
88Sump.liou.s o.f Newtonian mechanics. T o explain the ncw observations, a sequence
of new Id~, IlItroducoo in a more or less ad hoc fashion, were incorporated by sev-
cral phYSICISts. With the passage of time, and by the efforts of many brilliant men
these id~ cv?lved unt il they became what is now known as the QUa7UU/II theory, ~
theory w.hlCh IS, perha~s, the essence of contemporary physics. III this chapter we
shall revIew thc more Important experimental bases of quantum physics.
y
y
, which is thc same as the velocity of light in vacuum. We may sny that the wave
,
q _-- -r
,,
, ------;-- (i
o ,
x
x
z situation exists fo r a charge which is in accelerated motion. The total energy of the
Z
}' ig. 1- 1. E1cctric field of 80 charge atl'tst. Fig. 1-2. Electric and magne tic fields of
a uniformly moving charge.
1.2 Ele ctromagnetll! IIndlntion
Th~ cl~tromagnetie l!!.!:.craetion between two charged particles can best be de-
sen bed III tenns of the concepts of electric and magnetic fields produced by the
charges. When a charged particle is at rest relative to an inertial observer, the
observer n~ea.sures a field which is called the electric field of the charge (Fig. 1- 1).
However, If the charge is in motiOi\ rela tive to the observe r, he observes a different
field, cal ~ ed ~he electromagnetic field of the charge (Fig. 1-2). One component of
the field IS stIll called electric, while the remaining component is called the magnetic
field . Such fields depend on the velocity and acceleration of the charge relative to
th.e observer. Sill~ the separation of the field produced by a charge into an elec-
tne and a magnetic part depends on the relative motion of the charge and the ob-
server, we should speak only of the electromagnetic field of the charged particle.
Conversely, when a particle moves through the electromagnetic field produced by
(1.2
1.2)
Ele(/rQl1l.Clgllelk radicdion 5
other charges, it e.'(periences a force given by
F = q(E+ v x (B),
where & and (B are the electric and magnetic fields, respectivdy, as measured by
an observer who measures the velocity of the partieie as v. In this way we can
describe the electromagnetic internetion of charged partieles in terms of fields .
Energy is required to set up an electromagnetic fidd. The cncrgy per unit volume
of an electromagnetic field in vacuum is
, 1 , (1.1 )
E = ; fOS +?(B,
-"
where EO and 1'0 are the vacuum pennitiivity and !>crmeability, respectively.
T he energy of a 31alic electromagnetic field (that is, a fidd that does not change
with time) obviously remains constant. However, when the field is lime dependent,
the electromagnetic energy at each ,}Oint changes with time. The time variations
of an electromagnetic field give rise to all declronlngnelie wnvl;l which propagates
with a velocity
c = I/vfo;J.o .. 3 X J08 m S-I, (1.2)
carries the energy of the dectromagnetic field. This energy wh ich is carried by an
electromagnetic wave is sometimes called eieclromlJ{llle/ic radialion.
Since a charge at rest relative to an observer produces a static field, the cha~ge
does not radiale electromagnctis energy. Also it can be shown that a charge winch
is in unifonn rectilinear motion does not radiate electromaglletic energy because
the total encrgy of its electromagnetic field remains constant. A very different
electromagnetic field of an :LCcc!emted charge varies with time. Therefore
an acceleraled charge radiates electromagnetic energy.
T he rate of euergy radiation by a chargc q moviug with velocity v and acceleration
fI , when the velocity is small relative to the velocity of light, is
dE q2 a2 ( 1.3)
at = 01fE# .
One important conclusion is that, if a charge is to be maintained in accelerat.ecI
motion, energy must be supplied to compensate for the energy t~nsferred as radul.-
lion. T his means that when an ion is accelerated, for cxaml>le III 0. Vlln de Gmaff
accelerator or in a cyclotron, 0. rraction of the energy supplied to the iOIl is lost as
eI(,'etromagnet.ic radialion. This energy loss, however, is ncgligible except. a.t rela-
tivistic energies. Cha.rged particles trapped in the ea.rth's magnetic field, in sun
spots, or in disUl.nt celestial bodies such as the Crab nebula.also emit, ~d iation,
calk'<l 3ynclmJlro1L radialion. This radiation extends from radIO frcq\ICnCLCS to the
extreme ultraviolet.
 fJfockbody rodiplion 7
6 Th~ jou."do/kmf oj quatltum phy,iu (1.2 1.3)
,
If the particle is decelerated instead of being accelerated, <t, ( 1.3) still holds and
. . OSCI11'
The rMC of energy nuillltlOIl ates be callsc of the variation

of z with lillie. To obtain
J. 2 Th
the a\'erage rate of energy ra.tiiation, 11"1.' recall that (%~) ... - 2 ~O

.
the energy rndilltcd is that c.xcess which the electromagnetic field has as 11 result of us

q"","
the dccrca.sc in the velocity of the charge. For example, when II. fo.st charge such rus
all electron or a proton hils a target and is stopped, a substantial part. of its t01.91 dE).... - 12n0e3
((it
(1.5)

energy gOO!! ofT lUI radiation (Fig. 1- 3), This radiation is called deceleration rnddl..
lion, or more oolllmoniy brelll38lraMtOlY [from the German words BrtmklHlg (decel- . I . d I adiates energy atan a\'erage rate given by
We may say that an oscillatlllg e eclne llJoO I' r . Ii II l1ating with
eration) and SlraJdul1(j (radiation)!. This is the chid mechanism by which radiation Eq. (1.5) and lha~ the radiation oorr"elll)()nds to an elecvomagnetlC II' ( OSCI
is produced in the x-my luOc:s which are used in physical, medical, and industrial the samc frequency 3.S the dilJoOlc.
IlI)piicalioIiS.

Fig. 1-3. HlldiMion emitted by

a chnrgc which is dc<:e1cr/ltcd when
it hits the target in un x-ray tube.

Fig . I_I. l\1ollOehromati ~ ~nergy

density of blackbody rad)(l.tlon. ilL
different tempcratures as a fU1lctlon
of the frequency. ,
Frequenry

@ 1.:1 1I1fU~l.boil" "a,liation .

The energy radiated by a charged particle may be absorbed by ot.her charged
particles which arc subject to thc action of the electromagnetic field produced by Co nsider a cavity whose walls areat a . certain temperature. The ~tomsllcom~~~bg
d t' . al. thc same lime ICY alJ'>V'
the first particle. lIence we may describe the interaction of two charged particles t he walls arc emittillg electroUlagnetlc ra la 10 11 ,
II s. '1'1 Ie ...........
. d' t' fiold
ol-trom'gnetle ra la Ion ....
as an eltchange of energy hy means of emission and absorption of radiation. For ra d emit
lallOIl t,, by eth.nr atoms 0 , lnewa
0..""1.1""
c
h h .t reaches
example, the oscillating electron:; in the antenna of a radio broadcasting station OCeUI)ies the whole eavity. When the radiatIon tml>pcd WIt In 1 I' cB:\ I y the
y
radiate energy. Pnrt of this energy is absorbed by the electrons in the antenna of a ..... uilibrimll with the atoms of the walls, thc amount of ell1e,rgy eml;ledtlb di-
....... . h t absorbed by them. "lenee, wnen Ie ra
al?mS .1>C~~lli~:~; I~~~~~i~i::~I.~~U~~ith the walls, the energy densit~. of. the
radio receiver, which rcsuh~ in a signal at the receiving station.
An analysis of the processes of emission and absorption of radiation (that is, the allon Ill. e . E nent has shown that, at equlhbnum,
interaction of radiation and matter) is fundamental for understanding the beha.vior electromagnetic field IS ~nsta~l..\. ~xr~"a well-defined energy distribution; that
of matter. As we shall see in the following sections, quantum physics evolved as a
result. of the analysis of such I>rocesses. ~!let~r::~~!~:::;~~~~I;o~:aII~ds an energy density. whieh d.epen?~ solely 011
" mture of lhe walls and is independent of their material. II~e en.ergy
t Ie ~cnlpe ndill to radiation with frequency between ]I and ]I +dv IS wrL.tten
EXA MI'LE 1.1. Thr nile III which I'llergy is radis-ted by an o.scills-ling electric dil)()lc.
:~e(~)s~~ c~.~;::OE(V) 7s the cnergy density l)Cr unit fr~l.lcnCY, range, .soll "tl~:!Il,:~
$o1.. ,i()II : Consider 11 charge q moving lI\ong the Z-axis in such a way lhs-t at I\ny time , . 1'1 \ ed vnrmtlon 0 E(V) WI I II ... , ....-
called lIlo1!oclilomalic wergy dellsz/y. Ie 0 )scrv . C Ik these wero
ill! l}OSition is given by l _ %0 e~ wI. This corresponds to an oscillatory mOlion of aml)li- . 11"<t..... t--' ill Fig 1- 4 for two temperatures. urvcs I e b
wde lO Ilnd uligulllr frequency w. Thus the ehargc is equivalent to fin OIlcil1ating electric quency v lS I " ". 0..""1.1. I . 1899 I t may c
lir"t nbta.ined experimentally by Lummer nnd Prlllg8 lelln ~\ ,. .1 . pro-
dipole. The acceleration of the pllrticle i ~ a - -w~z. Substituting this valuc of 0 in sccn from the curves that for caeh temperoture 1he energy\.. e,ll>:ilt y s 101\ 8, a 'hich
Eq. (1.3), wc halc . , Note also that t"e requency a \\
nounced nlaxilllum a~ a certa1l1 rcqueney. . . This ex-
tho energy density is maximulll incrCl\.Scs as the .tell1l>croture merca:-cs.
(1.4) plains the change in color of a mdialing body n!:l Its temperature vanes.
 8 ThejoomiaiiOfl.f 0/ qU(J"lurII phy,ici (1.3 8/(lckbody r(ldi(llion 9
1.3)
If a. small hole is opened in olle of the walls of the cavity, some of the radiation
~worked ~ and because physicists at the time lacked a better e~Jllal.l.'\tion. We
escaj:leS and may be analytcd. The hole apllCars very bright when the body is at It. do not' Ilave abetl"r
high temperatures and the intensity of the equilibrium radiation within the caxity stili . . c,'(planalioll', we must accept the quantization of some
is high, but it appears completely black at low temperatures, when the intcniit.y )h sical lU\ntities as a fundamental fact of nature. .
I BY q" considerations of a statistical nature, together wllh Eq. (1.6),
of the equilibrium radiation is negligible in the visible region of the spectrum. y apl> ymg some I d' .on of
Planck obtained, for the energy density in blaekbo< y ra muon, an cxpressJ
l'or that reason the radiation comil1g out of the cavity was called blackbody radi","
lion by those who nnnl yted it in the nineteenth century. the fom1
The problem of finding what mechanism causes radiating atoms to produce the (1.8)
observed energy distribution of blackbody radiation led to the birth of quantum
physics. By the end of the last centu ry 9.11 attempts to explain this energy distribu-
tion using the concepts available at that lime had failed completely. The German where k is Boltzmann's constant. This expression , which agrees surprisingly '~
<l) physicist :>.Iax PlII.Jlck ( 1858- HH7) suggested~ 1900, that if the radiation in . . tal values of E{I') 0.1. different t.cm pemturcs, has bccn aceep
the cavity was in C(luilibrium with the atoms of the walls, there should be II. cor- With the expenmen. r hi -kbod,' ra<liation. It is called Pla nck', radialion law.
as the correct expres~;Jon or a" be 'd od
respondence between the energy distribution in the radiation and the energies of . . _ ""'t i, that Planck's derivation ca.nnot prcscnlly conSI er
An l1lten."Sting a"I....... . .) I h 'rd the
the atoms in the cavit.y. As a modc1 for the radiating atoms, Planck assumed that as pIlyslCll . " i, the reason we have olluttC(llt. not" er'loI cd
' I I y soun d ('''h'''''h s, b
atoms behave as harmonic oscillators, and that each one oscillates with a givcn pro) h
IIem W IIC prec
"p',t-I-"
.. "u the birth of the quantum theory.
was ,Irst
I so v y
t'l
frequency II. As a second assumption Planck suggested that means of an " unsatisfactory method. The problem had to walt severa years un I
the quantum theory was developc<l along other lines ~f th~ught. before ~n ad.eq~ate
each mJci/lalor can absorb or emit radiation energy ollly ill an amount thod of calculation was found. This revisC(1 deflvatlOn Will bc given 1Il ec-
7JTOpor/i01zallo ils frequency 1'. :7~n 13 G H owever Planck's ideas, especially Eq8. ( 1.(1) an<.l ( 1.7), pro.mpted new
thinkin'g 'by many o~hcr physicists who wcre working on the lIlterprc\:lUO n of other
T his latter condition is not rC(luired by the classical theory of electromagnetism
rcltLted phenomena; this led to rspid development of quantun~ th~~Y, Its
(as expressed by :'IlaxlI'el1's C<juAtions), which pemlits a continuous emission o r
I Eq ( I 6) we introduced an arbitrnry constant h, caned IlalJck 8 com;t.allt.
absorption of energy. Given thtLt E' is the energy absorbed or emitted in a single
val~c, obtai~ed by making Eq. (1.8) fit the experimental results for E(I'), IS
process of interaction of an oscillator with electromagnetic radiation, Planck's
assumption slates thtLt (1.9)
II = 6.6256 X IO- u J s.
E = hI', ( 1.6) Planck's constant is one of the most important constants in physics.
where II is a PfOl)Qrlionality constant assumed to be the same for all oscillators. . " 1 ' of blackbody radialion in
Hence, when an oscillator absorbs o r emits electromagnetic radiation, its energy f;X .. BII' Lf; 1.2. Express the .monochromallc energ} (eU~1
I
)
incrcasc:s or dcerca.scs by tLIl amount JII'. Equation (1.6) then implies that terms of wavelength.
501,, , ;on ' Sometimes it is preferable to eXI,re$! the mouochromatic. energy hdenS:IY. in
Ille energy of atomic O&Cillators is quantized. lerma of 'wal'elength instead of frequl'.ncy .. We .dcfil~ E(>') ,;;co~~n~.t~a~ee ;:I~~t~
..(>') cD. ... _ .,;(.) d". We introduce the nllnu~ Sign cau'iC II.
That is, the energy of an oscillator of frequency I' can att.ain only cert:l.m values, sign~, although t;(.) and E(>') are both positive. TllUS, s ince ~ ... c/ >', we hal'e
which are (assuming that the minimum energy of the oscillator is zero) 0, IIv, 2hl',
3hv, .... Thus, in general, the possible values of the energy of an oscillator of fre- d"N>' - -c(>..~
quency I' are and
t;(>') ... - 1::(,,) dv/cD. ... t:(~)c(>..2 .
(1.7)
,
Hcplacing ,;(,,) by the "alue gIVen It IIII '~q. ( 1.8) and setting" ... c/>., we finally obtain
"
where II is a l)(ositive integer. Aa we know, the energy of an oscillator is propor-
tional to the ~qUllrc of its amplitude and, 0. priori, by properly adjusting the ampli- Srhc I (1. 10)
tude of thc oscillations, we CtL!} make an oscillato r of a given frc<!ueney have any E(>') ... ~ ehl~~T _ I .

arbitrarily chosen energy. Therefore Planck's idca was an ad hoc a.s.5l1mptiOIl which
could lIot be explaillc<l by means of classical concepts; it Wru! justified only because The graph of E(>' ) i$ shown in Fig. 1-5 for different temperatures. I t sho\\'~ a llTonounced
peak ala Wtll'clenglh which dCI'.md~ on the \emperzllulC.
 IO TIlt! joulldaliorl.1f oj qtlllll/Um phy,iu (1,3 PhoIotkctric emi.uioll 11
/,4)

WI' observe lhat, R!! the temperature of the body increases, the peak of its energy dill-
I tribu tion is displaced toward shorter wavelengths, which causes a color change in the body,
Wi en's displacement law is thus very useful in determining the temperature of hot bodies,
such lLS o\'ens or slaTS, by finding the wavelength for which the intensity of the radiation
is Il maximum,
Wien's Illw Iliso gives a method for measuring h in terms of the eXI>erimental value of b
and its definition in termll of h, e, and k gh'en above, The conllistcncy of the results with
other melLSuremcnls of h ill another proof of the correctness of Planck'lI distribution law,
'''49''K
E}(AMI,,_E l.il, Obtain the total energy demJity of blackbody radiation as a function
of teml>eTllture,
J2WOK 50""';0/1' Since t: (,) d" is the energy density in the frequen cy range dll of the blackbody
radia tion, the total energy density is
109.5K
F. _
[ srh/''
E(")d ,, - - --
d
"3 ,,
--.
o 2 3 , , o c3 0v'/ U' - !
I L is obvious that E is equal 10 the area under tho curve .:(,,) of Fig, 1- 4, In troducing the
Wavelength /<.
variable x _ h"lkT , we hll.\'e d" _ (k T I II ) dx, and
Fig. 1-5. i\" o~ochro matjc energy detlHity of blackbody radiation at different tempera-
lures as l\ functIon of the w8.\-cJength.

EXAMPLE 1.3. Find the wavelength at which the monochromatic energy density of The "alue of the integral is 6.4938, and thull
blackbody radiation is maximum at II. given temperature. E _ aT", ( 1.12)
Solutioll' Let us use Eq. ( 1.10) and, to simplify OUT exposition, we shall setl: _ Iu:/MT, where
I!O that E().) becom~

~;(>.)
Equlltion (1.1 2) is known as tile Stt!fln-Bollzmann lmo, disco,'ered empiritally in 18i9 by
Josef Stean and proved theoretically Wy Ludwig Boltzmann some years later, using
th ermodynamical meulods, A calculation, which lI'iII be omitted, sho ws that the energy
To find the mlL:l:imurn of E().), we first find dE/dz and equate it to zero. The resulting emitted by a blacklxxly ]>er unit area and l>ef unit time, called its radialwn emiUalltt, ill
equation is gi" en by t' _ uTt, where <T _ U')ca _ 5,6693 X 10- 8 W m- 2 K-4 is called t he SU!an-
Boltzmann con4fan.!,
T he dCI>endence of E or F on T4 has been vcrified ex]>erimentally, From the measured
This is.ll. transcendental equation, which we solve by SUC<le$Sivc appro:dmation to obtain \'alue of fl or a we can recalculate II, again ob taining a consistent ,'alue, We can use the
% - 4.9651. Thw~). T ... b, where Stefsn Bolumann Illw to detcmline the tcmperature of a blackbody by measuring its
radiation emittance,
b - hc(4.9051k ... 2.8978 X 10-3 m"K h should be noled that most radiating bodie_such lUI the sun, an incandescent fila-
ment, or a hot gas---do not behave like blackbodies, and therefore do not rigorously
is called the Wien di,pl(la7l(~nt CCln8l alll. The expressioll obey the relations derin'tl in this section.
).7' _ b
( 1.1 I)
() 1.4 'huttHlt!etric jo.",I,.,1#41ft
constitu te!:! lriefl'6 di6p/ocemelltlaw, discovered 1896 by Wilhelm \\"ien, T his law states
r
that the ma'l:ima of ~:(A) (l.t diffe rent. tempef11tul'(!" l , T~, 1'3, '" f(l.11 lIt. wavelengths In 1887, while investigating the electric discharge betwecn two electrodes as a
AI, A:l, A3, ' , , such that source of electromagnetic waves, Heinrich Hertz observed that the intensity of
the discharge was increased whCl\ the elcct.rodcs were illuminated with ultraviolet
light, T his effect suggested that electrons were emitted from the illuminated sur-
12 TkjO!lluialion, oj quanlum phy,iu (1.4
1.4) Pholotllric eminion 13

faces. A year latcr Wilhdlll ll allwach.'J observed an electronic cmi~ion when he

may write Eq. (1.1 3) as
illuminated the surfaces of ccrtain mctals such as zinc, rubidium, l>Otassium, anJ
sodium. The])ro<:es.'J by which electrons are released from a material undcr the Et=hll-';. ( 1.14)
action of r..adiat ion is called IJ/wJrx/ectr;c em;!,;o" or IJholoc/edric effea. The emitted
Not all electrons require the same energy .; to escape from the metal. We call
electrons arc called plloloc/eclro'" because of the method of their production. The
electronic emission incrc&.sc!! with an increase in the intensity of the radiation faIl- the minimum energy value 4>0 the u.'Ork juncJion of the metal. Then the maximum
ing on the mctal surface, since more energy is available to release electrons; but a kinetic energy of the escaped electrons is
characteri~tic dependence on the frequcncy of the incident radiation is also ob- Bk mu = hll - <Po (1.1 5)
scrn!(1. This means tlillt for cs.ch substance there is 8. minimum, or threshold,
frequency 110 of electromagnetic radiation such that, no matter how intensc the From this equation we see that, at the frc<luency 110 for which
radiation may be, no photoelectron... are produced for radiation of frequency less hvo - II>IJ = 0 110 = 4>o/h,
than "0' The photoelectric current as a function of the frequency of the incident
electromagnetic radiation is shown in Fig. 1-6. the maximum killelic energy of the electrons is zero. T herefore 110 is the minimum
or threshold frequency at. which there is photoelectric emission. For frequencies
smaller than "0, so that hll < 11>0, there is no emission at all, since the electrons can-

,~
<
no t absorb enough energy in a single process to CSCal>C from the metal, regardless of
the intensity of the radiation. Thus Einstein's proposal very nicely e};plains the ob-
served dependence of the photoelectric efTcct on the frequency of the radiatio n.

Fig. 1-6. Photoelectric current as n I',

function of the frecluency of the incidenL
f3di3lion. J "
L __-O"~',","'''-ffi-'-'-'--- + -
E lN"tric field

Force On
eLectron c
In a mctal there are electrons which are more or less free to move throughout the
crystal lattice. These electrons do not escape from the metal at normal tempera-
ture because they do not have enough energy to overcome the coulomb potential
energy al. the surface of the melal. One way to increase the energy of the elect rons
is by heating the mctal. The ~e\'8.porated n elect rons are then called Ihenlloeleclron,.
This is Ihe kind of electronic emissiOIl that exists in electron tubes. However, as
the c;'(pcriments of lI ertz and I-Iallwachs show, another way to relcase electrOTlS
from a metal is to make it possible for the electrons to absorb energy from electro- Fig. 1-7 . Experimental arrangement Fig. 1-8. Hel!ltion between stopping p0-
magnetic r:ldiation. Let us d~ignate the energy required by an elcctron to escape for observing the photoele<:tric effeet. tential and frequency of radiation in the
from a given metal by 11>. T hen, gi\'cn that the electron absorbs an energy B, the photoelectric effect.
difference E - II> will apl>car as kinetic energy Et of the escaping electrOTl. lIence
we may write We can measure the maximum kinetic energy E t . mu using the method indicated
in Fig. 1- 7. By applying a potential difTerence V between plates A and C, we ean
(1.1 3) retard the motion of the photoelectrons. At a particular voltage 1'0 the current,
indicated by the electrometer E, drops suddenly to zero, which means that no elec-
Obviously if I~ i.-s smaller thnn <p no electronic cmission wi\] result. trons, noL even the fastest ones, aTe reaching pla\.c C. T hen E k mu = eVo and
In 100:) Albert Einstein proposed an explnnation for the dependence of photo- Eq. (1.1 5) becomes
ciccI ric cmiSj;ion on the freqlleney of the radiation. Einstein suggested tlJtI.~ free
eVo = hll - 4>0' (1.16)
electrons, in their interaction with electromagnetic mdiation, behnve in the $iLme
way I'lnnck prol>osed for atomic oscillatOr!! in connection with blackbody radia- By changing the frequency II, we can obtain 8. series of values for the stopping poten-
tion. ThUll, according to Eq. ( 1.6), the energy E absorbed by an electron in a sin~le tial 1'0' If Eq. (1.16) is correct, the result of 1)lotting the values of Vo against II
process frOIll elcctromllgnctic radiation of frequency v is t: = hll. T herefore we should be a straight line. This is exactly what is obtained, as shown in fig. 1-8.
 &all~r ing of f(J(liu/ioll b.v frtf tlte/rom 15
( 1.5 15)

The slope of the straight line is Ian ... = hie. i\1ca.suring a, and ulling the known o 00,,0,,1 not mention this problem at all. The reason is that, in the ease of an
IIOIl, II " . d
value of~, we may recalculate Planck's constant Ii. The result is the SiLme as that electron bound to either an atom, z\ moleculc, or a 8Ol1d, the energy an mOlllentu~
found for blackbody radiation. This agreeme nt can be cxlrlsidered as a furt/her ab!\Orbcd arc sha red both by the electro n and th~ atom, the 1ll?I<;tule, o~ the ,,?hd
justification of Planck's assllrnptioll involved in Eq. (\.6). f latlice to which the electron is coupled. In sueh clrculllsUu.lecs It IS alwa}s posslbl.e
From the observed value of vo, one may also obtain the work function of the tu ~!Jlit both energy and llll)mentUtll in the correct propurtlon ilO that both quantI-
metal, 4>0 = hvo, and compare it with the valuc of the work function obtained by ties arc cl)nscrved. However, the alom,
othcr means. The resul ts are consistent. OIolecule, or solid- each of which hns a
much lnrger rmWi than the electron- .... r-
]n";dwt
1.1 .~'nllfr;n" oillmliulion by "'r ee Ele ctrolllJ carries (along \Iith some momentum)
radialion
only z\ smnll fraction of the energy
So far we have considered only the tl1~rgy associated with clC(:tromagnetie radiation. II.vnilfible, so small that it is usunlly 1I0t
However, an electromagnctie wave carries momentum ill addition to energy. (This , colI"idercd at all. In the e!1SC of a free
is not sUf1>rising, since energy and momentum are closely related.) Noting that ele<:tron, since there is no other p..'lrtiele
electromagnetic radiation I>ropagates with a velocity c, we can show, using :\Iax~ 'filh which the electron shares the
well's equations, t1lRt the relation between energy and momentum for a plane energy and the momentum, no nb8O rp-
electromagnetic wave is tion or scattering should be pOiSSiblo
IIitho\lt violating the COnJ;crv!llion of
H = cp. ( 1.l 7)
either of the two quantities.
Bul. according to the theory of relativity (see Eq. A. I I), the energy of a particle
of rest Illass 1110 Slid momentum 11 ill

( 1.18)
This becomes identical to Eq. ( \,17) when 1110 = O. Hence we may conclude that
the relation between energy and momentum is the same for a plane electromagnetic
wave us for a particle of zero rest ma!>s.
When an electromagnetic wave is emitted, absorbed, or scattered, both energy
and IllOll1ent.Ulll aTe exehang(,.'(! with the particles responsible for the 1)tl)Ce!:lS. There-
forc whcn we analyze any process in which electromagnetic radiation interacts with
charged particles we must apl>ly the laws of conservation of energy and momentum,
being careful to take Eq. (1.17) into account for the part corrcsl>ond ing to the
electromagnetic wave.
This result poses certain problems when we consider the interaction of an electro-
mngnetic wave with a free charged particle, such as a free electron. If, for example,
an electron absorbs an energy b' from an electromagnetic wave, it must also absorb
a momentum l' = Bl c. :\'011' if wc assume that the free elect ron was originally at
rest in the observer's frame of reference, the absorbed energy becomes the kinetic
energy of the electron. But the kinetic energy of all electron is related to its momen-
tum /1. by
and this relation is incompatible wi th 1I~ = El c and HI;. = E, as rc<l uired by the
principles of conservation of energy anti of momentum. Thus we might concl ude
that a frec electron cannot interact with all clectromaglletic wave without violating
the principles of conservation of momelltum or of energy. The student may then
wonder why, when we were discussing the photoelectric eITect in the preced ing sec-
,"' i g. 1-9. Inten~ iL~' distribution of the
radiation scnuered by a free electron at
ditTe rcnL scatterin g anglt~.
Experiment, however, tells a. different slory. When we analyze the electromag-
netic radiation thilt has passed th rough a region in which frec electrons are pr~.nt,
we observe that, in additiun to the incident radiation, there is another rad~at~on
I)rcscnt, of differen t frequency. This new radiation is interpreted ~ ~he .radmtlOlI
scattered by the free electrons. The frC<luency of the scatt.erod radratloll IS smaller
than the frequency of the incident rndiation, alld aeeordmgly .th~ l\'avc1en~tl~ of
the scattered radiation i.~ longer than the wavelength of til: Hl~,dent radlatl?l1.
T he wavelength of the seatlerc<1 rndiation depends on the drreclLon of scattenng
(Fig. 1- 9). This interesting phenomenon is caJ1ed the Cmll/Jloll effed, after the
American physicist A. II . Coml>ton (1892- 1962), wIll) first obiscrved and anal yzed
it in the earl y 1920's.
Given that A is the wavelength of the ineidenL radiatioll and A' that of l~e ~t
tered radiation Compton found tlrat A' - A is determined solely by Ihe dIrectIon
of the scattcrir:g. That is, if 8 is the angle between the incident wavCR and the
 18 The joullIlo/iol1l oj quan/"", phYlin (J.6 Ph%lll 19
/ 1.6)
On t he basis of this interpretation of the Compton effect , together wi tb our pre-
Our .cxplanation ~f thc Comploll elTect. must. be carefully analyzcd because f i vious d iscu~ion of blackbody radiation and the photoelect ric effe<:t, we may con-
PO.'!8Ible rar-rcn.cllI~,g ('QIl;;CqIlCIlCCi. First let liS restatc our assumptions: Q ts clude t hat a photon is the UqlUlntumW of electromagnetic encrgy aud moment.um
(a) The scatterlllg of electromagnctie radiation by a fr...... "I-tm" I - enlittcd or abso rbed in a single process by a charged pa rtiele. I t is entirely deter-
u I II I
SI CJ"C( MaC() 1~lon >ctwccn the electron and .a partiAl-
~" ...." lJIay >c COIl- mined by the frequency of the radiation. Thercrorc, we may state the following
.. " 0' zcro res t mas::c.
~b) Elcctromagnctic rndilllion 1)lays the role of the particle of 2.e rt. principle:
which for brevity wc shall call a photoll. ro ClS mass, IVhen all eiectrlmuujllf!lic (("(WI.' irl/cractlf It'ith a charged Ilarlick, the
(c) IT heI cnergy and momcntum of the Imrticle of zc~, --I
, ......., m8.8S (
orI
I Ie p Iloton ) alllO!.Hlls oj energy alld momentum Ichidl are exchallged in the procelf8
are rc al(!( to the fre<luency and wavelength of thc electromagnet ic radiation by are UI03I.' correspondiny to a 1'/10/011.
J~' = /tv, fl = hi X. ( 1. 28) The principle stated above is one of thc fundamentallaw8 of physics. It is appli-
('able to all radiative processes involving charged particlCii and electromagnetic
. . relation i~ due to the fact. that
The sccolld ' p -- Ej, = hvcan{ j I vcj =- I/X We fields. It docs not. stem from any law that. we have sta te<1 or discussed previously,
may visualize the Compton effect a~ the collision i1Iustrate<1 in Fig I- II Ii but is a completely new principlc, to bc considered on the salllC level as such uni-
photon of frequency v cull ides with all electron at rest, transfcrin'g to i't erc.a vcr;;al laws as the conservation of energy and mo mentum. Thc discovery of thi~
CllCrlt.yII Illld momentum. As a rt'Sult of thc interactio"
' , tl,-.... sent1el1:< I p Iloton
ceTlam
has law in t he first qua rter of this century was u. milestone in tho developme nt of
11 "1110. er C!lcrgy, and a correspondingly smaller frequcncy v'. The elcctr{J1l aftcl"
the physics.
f tI scatterlllg,
. .I has
I a m<)lllentum equnl to t hc d ifferenA" ..." 1,-1
.. Ilccn. tl Ie momentum
' T hc eOI1CCI)t of t he photon suggests a simple pictorial representation of the
o ,IC. IIlCI( ent.II p \IIton . thuL of the .~en t tcr~"
. and .;u
pl,ot011. II' e call veri.y,thiS . fnct
electromagnetic interaction between two eharge<l particles, as shown in Fig. 1- 12.
eXp~rtfllcllta y. It. l~ a difficult eXI>crilllcnt but't I b f
r('~\llt~ c11C~k very wcll with thcor;. , I 1:1S cell I>cr ormed and the

~ttell.'l ,
-.... _-
photo" Alter ,.;
'"
.
.....

Fi8" .. I -I ~ . ;\lomclIlulIl and (,lIerg)" I

- ---:.:-.,.
//
... Fit!. 1-12. Electrom8t!nctic interac-
Intenoion .1'' '' ' ' ' ' ' ' ' \ / ' '' '8
Ineidenl
relations lU COIllI,ton M'at\cring. photon tion considered II!! 8n exchange of Jlha- .
Pt, I-;l tons. The I,hotons transfer encrgy and I~fore P ,
Elet'lron .. rlt'f" momcntum from onc charge to the
_lien,,!! other.

t"
Whnt is the physi('ul /Il('llning of thc photon concep' .",1 tl d fi .
( I ')8)1 J .
0' I
Ie e lllllig re a-
Ions ._ . t Ig nOI. a Il()CSSIlry conclusion thnt electromagnctic mdiation is a
The interaction corresponds to an exchange of moment.um and energy. T he initial
momenta. P I a nd P 2 of the Imrticles become P'I and 1)2 aftcr the interaction. Al-
IIt~m of I,holonll, willch c()I~ld be a 1)O~ible pictorial cxplanation. Bcferrin to though the interaction is not. localized at a particular instant, for simplicity we
\h~COml)lon effecl, wc lIlay Illterpret the photon energy r; = Ii" and mOI\l('n~um have indicated it at a particular time, and a t positions A a nd 8. P article 1 inter-
7 - hi >' as the cncr~y and mhmentum absorbed by the frcc electron from lhe ill ._ acts with partiele 2 via its electromagnetic field, with the result. that particle 2
dell
I' _L electromagnetic
'IX" I wave. The photon of CllC.......,..." I", -- h'
v all(I momentum " takes a certain amoun t of encrgy and momentum from the field , equivalent to a
~ - I IS ~ l~n tho cnergy and momenWm rc-emitted by the c1cctl1)Jl into the photon, with a corresponding cha nge in its motion. T he mot,ion of particle 1 must
"catter~ mdlatlon. I n other w{Jrd.~, wc lllay consider that the Compton elTect tllen be adjusl.c<i to correspond \'0 the new field, which is the original ficld millus
occurs III LII'O steps: fihlt u photon of encrgy hv is abso rbed by the clect ron and one pho ton. Of course, t he revcrse process is also possible, a nd particle 1 may
ufterwa rd the electron emit.'! n photon of energy /iv'. T he eleetron ncr uire k.' t
cncrgy E
~Ir =
E' r
- ~ all{ I a momentum I'. = I) - p', which nrc related I sa lIle IC
by
absorb a plloton from the field of Ilart.icle 2. We muy say then that what has hap-
pened is tilat, bet ween particles I and 2, there hIlS been an exchange of phokms.
I n othcr words,
Ek "'"' cVm~2 + p! - moe 2 ,
dedromaglletic ilileracli0118 call be pidured as being the result of the
as rcquiJ"C(1 by the conl'{'rvation of energy find lllomentum. exchange of phO/OliS betu;een interaclirlY .;hargtd 1}(Jrlicit8.
 20 T~ joundalionl oj qUCUllum physics
(1.6
,.~
Phololl3
"
t'req~ncy, Name of Photon 'r---'---'---'---'---'--'
'" radiation ene'XY, eV Ch&nlc~tie
radiation
my. 10-" I X-unit, XU 5 ~--e----+----+----4----~
IO- I?
r--.~---..-------L,~ 10- 11

IO"-J:::=::::~=:=t 10' 10- 1 _ 1 ."ptrom. ,j,

1-
,"II "" 10-'- 1 nanometer, nm

::::':),.mo,.....~~..mo...,.,='O
"" "
10- 7
IO-e_ l mieron,
IOI~ I'

IO- ~
10 13
,,~
J01 ~ 10-'
1011 10-3 IO-~

IO-~ lO-l_1 t'e!ltin'et('r, ,m

10-1

I ()O - l meter, III

'"HI'
l ()l - l kilometer. km Fig. I-I I. Intensity distribu tion in the x-ray IIpectrum of molybdenum as a function
of the applied voltage. The K-series e~citation I)()tentiai is 20.1 kV and appears as the
10' 10'
characteristic SI)ikes on the 25-k V eUrle.
klll- l()3 10'
Therefore
Fig. 1-1 3. The electr omagnetic sJ)Cjrum. E .. 1.2397 X IO- 'f). ... 1.2-1 X 10-'/ >",
where E is expressed in electron \'ol~ and). in meter.t.
At any instant, the total momentum of a system of two charged particles is As we explained in connection wilh Fig. 1- 3, x-rays are IlrOdllced by the impact of f3.!it
electrons against the anode mucrial of an x-ray tube. The energy of an electron may be
I"lIdiated as II result of sUCXleMive collisions, so that SCI'eral photons are produced; or it
PI + P 2 + f'field, may all be I"lIdiated !1.9 a single photon in j~t one coJli"ion. Ob\'iously the most energetic
photons coming out of thc xray tube would be those emitted by means of the l!t1er
where PII6Id i,s the momentum associated with the electromagnetic field of the process, and these photons have the shortest wal'elength. In other worda, gil'cn that r
cha~':Ked particles and the t0t:n' energy is E I +
E 2 + E 1Mo1d _ is lhe accelerating I'oltage (in volts), which i! also the same !1.9 the energy of the electrons
<XI
bgure
0
1- 13 show9
.
the varIOus
I'
regions of the electromagnetic S........
... ~...
trum ,\\1,'th th e (in eV), the wavelengths of the x-ray! produced are equal to or longer than the threshold
mm n ,names given to cae I regIOn. The wavelength, frequency, and cne of wavelength, satisfying the relation
the associated photons are also given. rgy
J.2-1 X 10-'
).0 .. V m.
f:X.AMI:Lf~: ~ .5. ExpreSll the energy of a ,)hoton in electron volts in terma of its wnvc-
length gl,ven m rncUlrs. ~se the result to obtai n the wavelength of x-rays in terms of th For example, in a television tube, electrons arc accelerated by a potential difference of
aeceleratmg voltage a.pphed to an x-ray tube. 0
the order of 18,000 V. When the electrons rClleh the screen of the tube, they are abrulHly
Solutio" , From E .. h~ and >..~ - e, we have that ' - he/X. But stopped. Thus a television scrccn emits ~rays for the same rcason 3.!i an xray t~.
(The intensity, however, is quite low.) The minimum \\'al'elellgth of the x-rays produced
he .. (6.6256 X 10- 34 J s)(2.9979 X lOS m a-i) .. 1.9863 X 1O -2~ J m. when the electrons afe SlOl)l)C(i al the screen is ). .. 6.9 X 10- 11 m. The above rclation
ha.s bccn,.confirmed experimcntally. Jo'igure 1- \4 shows the intellsily of x-rays from an x-
ray tube as a function of the wal'clenglh of the cmiued photons for different values of V.
Remembering that 1 eV .. 1.6021 X 10- 19 .1, we see that he .. 1.2397 X lO-eeV m.
 " The jouflJaliolJI of quanlum phy,ic,
(t.7 23
1. 7 S iolitmnr" lit/a/,."
T h fact that only ccrtam - rrequenClcs
. ''It JI~, v3 , " ''II'C olcrved in emission
When an electromagnetic wave interacts with a system of charges, such lUI 8n B~'<Orption can be eX I)\:)'ined if we russUIlIC that the energ,v of ~hc atom can have
atolll, Il molecule, or a nucleus, the electric and magnetic fields of the WS\'C disturb I
Budl ccrtrunvalle.sr~
. ,- I ' E' 2, E-3, Fach
~
allowe<1
. energy
.. . I~ called
value bso'an ellu9Yr
the motioll of the chn~;;. J.!.1 the language of classicat physi~, we could say that OIl ~ 1'1 en t he on1y possible fre<luencies wluch result. 1/1 enUSS10n or a rpUon o.
the wave impresses a forded oscillation on the natural motion of t he charges. This lr!~ . I
rfUJiauon arc
those corresponding to transitions betwccn two allowed energy levels,
' . be ._, r II _,_
remits in o.b;;orptioll tJ energy by the system of charges. A clll&l.ical ():SCillator that is, JI = ( E,- - B,)/II. T hus Dohr's flSSlWlpllOll Illay stllt..'U as 0 0\\ .
I'($I)(mdl:l most easily when the frequency of the forced OSCillatiollS is t he SAme as
i11:1 natural free/uelley, a situation which is called re~naTlt:t. When there is res0- The energy of a S!lsiem of cJ,arfJfl,_itiler all ajo~n, a I/lolecule~ or a
nance, the rate at which t he oscillator abso rbs energy is maximum. nucleus-calt IImoe ollly cerlailt l'(J/ueS Bit 8 2, E3 , . ; thal ~8, the
I t has been found cxpcri rncillally that atoms, molecules, nuclei- in general, any energy t8- quan,-/.leer. ,'I,e state, correspondillg to these elierY/CIl ared
n.sscmbly of cha rged particles- have a serics of reson31ing frequenciC$ "I, "2, ,,~, ... called stalionary slate8 mid /he 1108sible t'altu!s oj fhe entf9Y are calle
IlL which the abao rption of electromagnetic radia tion is al>p reciable. Ai all other energy levels.
fre<luencics the absorp tion is negligible. T he resonating frequencies "h "2, "a, ...
constitute tile absOrfiliOl! Spec/rum of the substa nce. Let. WI fl8$ume that t he system Absorp t ion of electroma~netic radiation, or of any ot her energy, res ults in a tran-
initially hlUl a most stable state of minimum energy, ealle<lthe ground slate. T hen, -- of the atom (or molecule or nucleus) from one stationary state to another of
when the system absorbs electromagnetic radiation, it pili!S(';j to anothe r stale of ~ltlon energy; emissioll of clectromagnctic rn d-mtlon
higher - I'CSII It.s -Ul . tilC reverse
;' ]lrOCCSS)_

higher energy, called all exdted 8lale. I n the case of n clnssicnl oscillati ng elect ric The frequency of the radiation involved in the proccss IS gIven by Lq. ( 1.29 .
dipole, an excited state would correspond to a larger a mplitUde of oscillation.
Obviou~ly a system of eharg(';j in all excited state lllay release its excess energy
in the form of elcct romagnetie rad iation. T he frequencies observed in the radiation [ ~: ====t==t=
====++ I
emitted collstitute the emission 8pectrum of t he system of charges. K" I>eriellce has
showll that.
1';3 ---,,,-t-'-
Ihe frtquencits ob~rrJf'd in Ille a/norplion speclrum of a s!l81em of
K, -~i-''--'--
cJ,ar~8 arc alfH) omerr.'ed in Ille emission Speclrwn of I~ syslem. Fig. 1-1 5. Transitions .bet"ccn
stationary states. The relative spac-
For example, sodillm atoms show preferential absorption fo r light of frequency ing of the energy le"els lind lhe [>OS-
~[lIal to :i.O!) X IOJ.! li z or wavelength equal to 5.89 x 10- 7 m. T hese a rc pre- 8ible transitions depend on the nature
cisely lhe valuCIJ of the (r('(lucncy and wavelength of the yellow light emitted by of the system . K,..JU _ __
incandC!!Cellt sodium vapor.
(b) EmllJllion
The existenCe of Ilspectrum composed of wcll..defined frequcncies was a problem
that puzzled physicists at the cnd of t he last celltUry and the beginning of this olle. Some transitio ns are shown schematically in Fig. 1- 15. A 1>1'OCCSS in which an a~o:
To IlOlve this problem, Illlew a nd revolutionary idea was adva nced in 1913 by the in its groun d state, represented by A, abllOrbs a photon and passes to an exC11
Danish physicist. Kiels Bohr (1885- 1962). Bohr used the photon concept as ana,.. state, represented by A, is dcsi~nated by
IY1.ed in t he previous section and extended Planck 's assump tion as expressed by
Eq. (1.0). SUPPO&C that an atom in a state of encrgy H abllOrbs radiation of fre- A+Jw-A.
quency JI and thwl passes to anothc r state of higher energy W. The change in energy
of the atom is N' - B. On the other hand, the cnergy abso rbed from the radiation Thc reverse proccss, photoll emiS.'lion, can be exprcssetl hy
in a single procc!;!! must be ~hat of a photon hv. Conservation of energy req uires
!lUlt. both quanti tit'S be equal. T herefore A --+ A + /!v.
H' - fI' = J,,,, (1.20) T he idea of systems of chargcs having only a diserele set of stati?nnry states is
completely foreign to llewtonian IlH.'Chanies. By th(' lawl! of IlcwtOlllan mcc h a!~I~'
an CXIHC!lSioll clllle<l 110hr's formula. Similarly, if the atom ]>asses from a statc of
the motion of a particle is determined by the initial conditions of the part.lc e,
cncrgy B' to another s tate of lower cnergy, B, the frequency of the emitte<l mdia-
tion must. be gi\'cn by Eq. (1.2!l). which arc eon.sider('(\ arbitmry. T hul:l a I>urticle may hav<, any ~n crgy, d~tcrmll.led
by the nrbi!mrily chosen initial conditions ( P()~ilion and velocIty). Tlm~ 3PllhC!!,
 The /ool1doliotu 0/ qw:ltllum physicl Siolionary slales 25
(1.7

for example, when an artificial satellite is placed in a stable orbit. An astronaut .. m"y n"cur between two slates of the discrele energy spectrum, such
TransitionS " ...... . d tal
may arbitrarily change the orbit, and thus also the cnergy, of his spaceship simply -"n
8ilaband LUI F,g. 1- 16, or between a slale of the dIscrete spectrum I an as. e
by changing thc velocity at a particular time. By the same loken, ncwtonian of the con , .IIIU 0"...., ,~.'rum
._-,
,uch as ei, or betwccn t\\'o slatCll of tie contmuoUS
mechanics allows the electron in a hydrogen atom to have any arbitrary energy, ~pcctr\llll, such as yk. 1
depending on the kinematical conditions that exist when the electron is captured
by the prolon to form the atom, and the electron could change its orbit by absorb-
ing an arbitrary amount of encrgy. Nat.ure, however, appears to work differently;
ollly certain motions arc allowed, or possible. In other words, the existence of
stAt ionary StAtCll must be accepted as a fundamental fact of nature.
The acceptance of the idea of stationary states pOSCll another difficulty within
Continuous
energy
spectrum
I

1,
E- O
the framework of classical I>hysics. When an electron revolves around a nucleus d
in an atom, its illotion has both tangential and centril>ctai accelcration; i.e., its
motion is accelerated. Therefore one would think that the electron would be Fig. 1-1 6. Origin of the discrete.
radiating energy continuously. As!l. result, the electron's energy would he decreas-
ing continuously and its orbit would be shrinking. This would make the eJ(istencc
of stationary stales impossible. However, neither this contraction of malleI' nor
and continuouS ~nergy spectrum
due to discrete stationary 8Ia~.
.
D~rete

~""
apeetfllnl

the continllOus radiation of encrgy associated with it. have been observed. T hcre--
fore, since the predictiolU! of elassical clectrodynamies are not followed , we may
conclude that an electron (or a charged particle) moving in a stationary state is
govemed by some additional principles which we have not yc~ considered. We
shall explore these ncw principles in Chapter 2. " ,
Boh r's assumption of stationary states was made on an ad hoc basis, withou~ ,.;y;t.1IPL. 1.6. Energy and momentum conl!er\'ation in radiative transitiOns.
any finn theoretical justification. The sm:ecss of his hypothesis, however, I>rompled $o/,lIio1l ' At first sight q. (1.29) i~ correct insofar a.~ energy. conl!ervayon ~s concer~d.
other phy!'icists to perform eJ(pcriments to test t.he idea. Quickly there acculllulated 1I0ll'el'er, a cI()I!er examination indica~ that it require~ a illIgh.t nl(){I.I~cllllon. In ~
a great wealth of infonnation, from which new and unsuspected atomic properties
. \\e no _.....:u1 that a I)hoton carries a momentum hf}.. - hll/c
. 16 '
1I0a .
III addi tion to the ener&)
..1' . .. s from
were discovered. This same situation has occurred several other times in contem- IIv lind that both momcntum and energy mu~t be conservcd III r..... laUve tra.n~l!Ion
porary physics. A physicist, with great intuition and courage, proposes a new and on'e state to another. Let us first oonsider emiuion by lin atom lit rest. T I11~11I1l~, before
bold concept; the idea provokes new thinking and experiments, and soon new and the transition, its momcntum is ~ro. ,\fter the transition the atom. must reCOil II'llh ,a mo-
unsuspected vistas arc OI)Cncd. mentum equal and op[l()sit.e to the momentum of the photon; that 18, 0 p ...... + I """",B
The stationary states do not necessarily constitute a discrete energy sl>cctrum. or, in magnitude,
In Illany instances all values of the energy in a certain energy range (or band) a re ( 1.30)
allowed and a continuous energy spectrum results. Let us consider, for example,
the case of an electron and a proton, and take the 1oero of energy when both the ~oll' let us consider ellergy conservation. Initially we ~ave an a.tom at rest ina stationa?
electron and proton are at. rest and arc separated by a very large distance. Then atate of energy f.'; and after the transitiOl! lin atom III a statIOnary state of energy . ,
all stationary Slates of negative energy, whieh correspond to bound states in with kinetic encrgy p~ .... / 2M and a photon of energy 1111. Therefore energy conservauon
which the elcctron moves around the proton to form a hydrogen atom, are quan- requires that
tized and the cnergy of such statC8 can have only certain values E'", B 1., EM, ...
(1.31)
(Fig. 1-IG). On the other hand, the states of positive energy are not quantized,
and their energy may have any value. These states are unbound and correspond
to the situation in which an elect ron is thrown, from a very large distance and with or, using Eq. ( 1.30),
a certain initial kinetic energy, against a proton; the electron, after passing near the
prolon, is dcflected from its original direction of motion and recedes to 3n infinite E; - E, - II~ (I + 2,~;C2) (1.32)
scpa ration without the formation of a bound lJystem. The energy of tho system
in this ellSC is detel'mined by the initial kinetic energy of the elcctron, which may Whcn b i8 "cry small compared .... ith 2.lfc 2 , the la.;;tterm ig negligj~l~ and Eq. (1.32)
be arbitrarily chosen. _.. E ( 1211)
",uU C('SlO q. . . 'I'hi, is the ea:'lC for atomic and molecular tranSlllOIiS. In general,
 ----------------~ ....................-
26 Th~ !oondo/iolJl of quuntum physiu
(1.8
/.8) EXMrimtnlol qidmu 0/ ~1(lIiOllary ,Ialt' 27
h" is smaller than .11c 2, and we ma," write Eq . (132)
.
,
In t Ie form
of tbe projectile is transferred a.'1 internal energy to the target. These arc called
h" - ( EI - E/ ) (I + 2)-1 _
? hIt
_.lIe
(1::,. _ E )
I
(I _~)2.1fc 2 '
inelastic collisions of the fir.' kim}. Inelastic ool\isiolls of the ucolld kinct correspond
to the reverse process.
II'h('re \I-e 11IH'C U51.'t1 the eXIIllnsion ( I +
.1') - 1 _ I _ + . Suppose that a fast particle q collides with another system A (which may be an
alOm, molecule, or nucleus) in its ground s tale of !'nergy B t . As a result of the
quantity amn II COJII]J8re<1 lI'jlh unity In til I x . " wHh % - 11./ 2 .1/(,2, a
resuhing ill . e 1U:It term we can replace h" by HI _ /<.[ , projectile-system interaction (which may be electromagnetic or nuclear), there is
an !'xehange ot energy. Let E2 be the energy of I he first excited state of the system.
(/':; - Elf
Ju, - E,. - fo'l Thc collision will be clastic (i.e., thc kinetic ellergy will be conserved) unless the
2.11c2 (1.33)
projectile has enough kinetic energy to tmnsfer the excitation energy 2 - EI to
where the last term is essentially the recoil en f , the ta rget. When this hapl>cns the collision is inelastic, and we may express it. by
I ergy 0 t Ie atom Therefore' h ..
prOCC-iS, t Ie energy of the ('milled phOlo11 is sli hI! I !. . ,In I C Cml8l!IOn
two energy levels of the emitter (atom mol ~ y css t Ian the dIfference between the
coil energy of the emiller. ,eeu e, or nucleu~) . The ditTcr<'ncc ill the rc-
On the other hand, for the absorption process we mus t modir,- f ( 131 ) ' .. When' he mass of the projectile q.is very small compared \\'it h that of the target A,
, .. q. . Jy \\'rltlllg
lIS happens for the case of a n electron colliding with an atom, the condition for in-
gi+h" - l\i +~ , elastic collision (sec Example 1.7) is
W (I ~
( 1.36)
since there is now n photon in the initial state but I ot' h
momentum requires that f' _ /' .h., I . lil. t e final stale. Conservation of
., . "O~ pho'on, \\ Ie I aga/ll IS equivale t t E where Ek = !m1l 2 is the kinetic energy of the projectile before the collision. The
II len \\(l use the Mille npproxlillation.\.!! abo\'e E II 0 q. ( 1.30). So,
, . . q. ( 1.3..' ) [)Ccomes
'"-
kinetic energy of the projectile after the collision is then E/. = Ek - (E 2 - E ,),
aince the energy lost by the projectile in the collision is E2 - HI'
h~ - (t.! - E,) ! __h,_) -' To give a concrete example, suppose that an electron of kinetic energy E" mo \'es
( 2Jfc 2
through a substance. let us say mercury vapor. Provided tha.t E.'k is sma.ller than
the first excitation energy of mercury, E2 - H I! the collisions are all elastic and
the electron moves through the v8l>or, lQ.'Jing energy very slowly, since the ma.."'<i-
(1.35)
mwn.kinetic energy lost in each collision (see P roblem 1.5,';) is al)proximat.ely
Therefore, for absorption to take place the ene of th
greater than the energy difference bet~.et!n Ih~ I e nb30rbed photon mus t be slightly
the kinetic energy of the recoiling amorber. "'0 el'eb of the absorber 10 aCCQunt for
A conacquence of this analysig is that a I)hoton em' ed However. if Ek is larger than E2 - E" the collision may be inelastic and the elec-
or nucleus) in the tran5ition (I __ b cannOt be !!.bsor~ by a syste~n (al.olll, molecule, tron may lose the energy E2 - E, in a single encoullter. If the initial kinetic
order to undergo the reverse transition b __ a , I th f by anoth~r ~dentleal system in
d . I energy of the electron was not much larger thall K 2 - t: I , the energy of the elec-
I enllCS to the aU!IOrl)tion slICctrum
. ,,', ~'Ila ",n(
come to
ere ore
. the emlSIJIO
thIS matte . n SlICe
. I'
Irum .IS not
For atomic and molecular Iransition.1 in which E _ E.' r agalll III ~xample 1./0. tron after the inelastic collision is insufficient to excite other atoms. Thereafter
and .lfc2 is of the order of lOll eV th .I J, I~ of the order of few electron l'Olts the successive collisions of the electron will be elastic. But if .hc kinetic energy of
10 ' e correction term III J;;"'s (I 33) I (I . thc electron was initially very large, it may still suffer a few morc inelastic colli-
IO- eVand thus is n{'gligible. On the other hand f -" " . ~n( .3S) 18 aoout
be of the order of 106 eV Sin ..... 1/,' ,., f 'h ' or nuclear lr!!.nSltlons, t.j - t:i may sions, losing the energy E2 - BI at each collision and I)ro<\ucing more excited
. ~~, 0 e Mille order as'n t ' ..
rectlve term is abollt 10 eV which is relatil'" . I a OllllC tran~lllon s, the Cor- atoms before being slowed down below the th reshold for inelastic collisions.
, y more Iml>orlant.
This process was observed for the first time in 101 1 by Franck and Hertz. Their
experimental arrangement is indicated scherllltticlilly in Fig. 1- 17. A hea led fila-
1.11 1::'lHrlll".III111 /<..'.:i,h'n,'f' til SI-I' S
. onary Ittlf'''' ment. F emits electrons which arc accelerated toward the grid G by n. variable
So far \\'e have introduced the idcn of stationa . potential V. T he space betwecn F :lnd G is filled with lIlC'rcury vapor. Betwccn the
explain the disc rete spectrum of atomic syste ry states as a conve.mcnt concept to grid G and the collecting pialI' P a small retarding potential I", of approximately
tions bet.wccn stlLtionary stales is amply co m~ H~vever, the eXlstencc of transi- 0.5 volt, is applied so that those electrons which are left with very little kinetic
lllQ.'Jt characteristic is that of inelastic colii/fO .rat h' by many experiments. T he energy after one or more inelastic collisions eanllot reach the plate and are not
Ions, 11\ IV teh part of the kinetic energy registered by the galv8nometer. As I' is increased , the plate current I fhtctuales
 28 Tht jOl.mdaliofU oj qurm/llm physict
(1.8 tJI InltNJ~lion of radialiall with mailer

--. .,- r I' if E I is the energy ot the initial stationary state of the larget and [0.'2 the energy
Slnll .... ), f ' sthat
of the linal ~tale, the oonser\"ation 0 energy require
+-
--_P cl p
2~ p2 + EJ - 2~ p,2 + 2~1 p2 + E2
:.rem.ry l
'_,lOt I

~ .
I
ok<C--t'---~IO'----'lt,---v
Volts
Fig. 1-17. Frnnck lind I!l'rh eXjlC:timent.al
srrang<!mcut for IInflly~ing inelllstic collisions Fig. 1-/ 8. E lectron Current versus at--
or the !iCcon<J kind. eelcr&ting potential in the Franck-Herb
experiment. mo
L'C),I-nl+M'
lUI shown in Fig. 1- 18, the peaks occurring at a spacing of about 4.0 vatu!. The
first dip corrcsJlond~ to elcctrons that lose all their kinetic energy after onc inelastic And therefore
collision with a mercury atom, which is then left in an excited state. The 8CC()nd mMv ,lip
dip corrC!Jponds to those electrons that suffered two inelastic collisions with two P -111+ ,11 - m+M'
mercury atoms, losing all their kinetic energy, and so 011. The excited mercury
atoms return to their ground Slate by emission of II photon, according to Hg- ..... equations which are, of course, eom.pati~le w.ith ~. (1.3?!. Substituting these valuC$ in
Eq. (I.38) after a straightforward 1Ilmplilicatlon, I'oe obtai
JIg + hI' with h/l = E2 - 8,. From sPectroscopic evidence we know that mercury
vapor, whell excited, emits radiat ioll whose wavelength is 2.536 X 10-7 m (or
2536 A ), COlTCSl>onding to a photon of energy hv equal to 4.86 eV. Radiation of
_.1_,
m+M 2m
(-.!.... p2) _ OS
this wavelength is observed coming from the mercury vapor during the passage of
the electron beam through the vapo r. Thus this simple experiment is one of the 1 ,
Illost striking proofs of the existence of stationary states. E. - - p (1.39)
2m
Another similar eXI>eriment is the coulomb excitalioll of nuclei. For e.xample,
Th' .. the threshold kinetic energy which lhe projectile must have for excit,.
ingISt:~::e~ ~v~ lirst excited level. proj~e~ile i~ ~uch.lighter th~ ~~_e .tar~l~:
when a l>ro tOn 1>as8C!J near a nucleus, the electrical interaction between the two
may give risc to an inelastic collision, resUlting ill the excitation of the nucleus to If the
m I/then ....e have Ek "OK ' ' ' E, - ", . ThIS IS the SituatIon for an me"",tlC
1 . 00 f hI
tom or molecule; we used this ~ilUation in Ollr ana YSls 0 t e
One of the lowest excited statcs. The nucleus returns to its ground slate, emitting
. " I th
gamma-ray I)hotons which have an energy of the order of several keV. For that
reason coulomb excitation i:; one of the most irnporUint experimental methods for ;~:n~~~I~e:~ze:~;i~e:t~ a Ho ....ever, .... hen nudei undergo coulom~L:x~~~~070~~~~
detecting and analyzing the low-lying stationary states of nuclei. of their inellllltie collisions ~'i th p~o~ns, ~'e m.UJlht usc ~. (ii~~):n~ not be small .... hen
that, in general, especially III colliSIons With hg t nue el, m . y
compared Wilh nnity.
f;XAtII l'J. 1.7. Calculation of Ihe threshold kinetic energy required for the excitation
of the target in aa inelastic collision of Ihe first kind.
1.9 Interactiun of fla,lIfttion " ,Uh jUntt"r
Sol .. 1;0.1' Let us (Iesignate the of the projectile and the target by til find M, resllollC-
The interaction of radiation with ~atter is one of the fundamental Proccsscshr~po~~
mil.'>!!
tively. We flSSUnl(' thflt the t!l.rget is initially at rest in the laboratory or IArame of
reterente. Given th:Lt p iii the mom('ntum of the projectile before the colli~ion and ,,, sible for many phenomena occurring in the unive~e: For example, the ~~h IS s~~
and J' the momenta of projectile and target after the colliSion, the conservation of 100- jeet to a continuous flow of electromagnetic ra<liallon fro.m the S~l1l, ~ ~c m~.
meutuIO requirc~ thfl~
life on carth possible through the pfOCcsa of pllol.a&Ylllhtns (th.at IS, t ebo0~~a :~n
f
p - ,>' + l'. o new eompoun d s, nUlln1y carbohydrates, out of the synthcsls d of lied
car chlorophyll
11 IOXI e
( 1.37) and water as a result of the absorption or photons; a eompoun ea
 --------~--,-------------
30 The/OUIII/uliom of quantum p hYlics
(1.9 1.9) Irlluarlion oj radiation wilh mal.1~r 31
plays nil important role in the renction). T he process can be written as
eculc. We may write the process as

A + III! ...... A+ + c-.

The nUlllber II of phOtOll8 involved is not fixed; their energy falls mostly in Lhc
. . . . I uivllicnt of the ]lholociectric effect in
visible Il.!gio n of the spectrum. The process is much more complicated than the This process, called phIHOlOllllatlo~, IS,t IC eq ',' "' fllso called thc womic pllOif)-
abo ve equation would s uggcst and aclive resea rch 011 it is still going 011. Photo- . sscd' Sect"10n I 3 I'or t lilt reason ~
metals dlscu 111 1 f . hotoioni7.11tion when II beam of ultraviolet, x- or "')'_
synthesis is important not only because it produces carbohydrates, which are the dec/ric tlTect. As a resu top 'l P~OdllC~ ionization along its path. Let us
ultillltltc source of food (and thus of energy) for most living organisms, but also radiation passes throug I .mlltter, I ,Iectron from an atom or molcculc by
because it controls the amount. of oxygen in the atmosphere by liberating oxygen, h ........ ulrod to extmc~ an
dcslgnate t e cllergy .~"
, ..
. . . .ovJ f" I Then the klJlctlc energy 0
r th e
which, 011 the other hand, is quickly consumed in the many oxidizing procCsscs I ' this encrgy is called the lOll/lallO!! 1,~t:1! /a.
occllrring 011 the carth. cj~tcd electron is given by
PhotOSYlllhcsi., is just one example of many reactions initiated by the ab80qltioll
E4 = hI! - I, (J AD)
of rauiation. The study of such reactions is called photochemistry. Each photo-
chemical reaction requires the intervention of photoils of a certain energy. Another
an equation analo.golls to Lq. '. n') E( m\tiOll ( 1.'10) show~ that, in order to
. ~ (I 101) (In this equlltion, incidentally, we havc
example of proce&scs due to absorption of radiation is t he diSSOCiatio n of a mol-
ecule by the IIbsorption of a photon. T hat is, ncglected the ~cc?ll ~lIergy of the IOoi the !hOtOll lllust be equal to or large~ than
produce photOlolllzatlon, thc el~crgy t' I "tatc. initially occupicd by t hc cJected
AB + III! ...... A+ B. I . The value of 1 depcl\(~~OIl t Ie sta l~nary b 'ccted from thc ground statc in a
7
electrons. For cxampl~, .If an electron ~~c ~h~tOIl must bc 1:-\.6 cV. B ut if the
One such reaction, of great. geophysical and biological importance, is the diSSOCia_ hydrogen atom, the 11111l!.lllUm energylo 3 -I ~r arc re( uircd. For heliUlII atoills the
tion of oxygcn in the atmos])licrc by the absorption of ultraviolet radiation of wave- ck'Ctrou is ill the first excIted state, 011 y ci(!C~ro;1 f!"VIllI the ground s late is 24.6 cV.
length in the range of 1600 A to 2-100 A (that is, I)hotons with an energy between ioniza1ion en.ergy needed to rClllove ~ll r calk'd the iOU08/1 , thc largc concen-
here
7.8 cV and 5.2 eV). We Illfly express this process by the equation In the rcglon of the upper al111o:lc ClO l1 >er m3) is due most ly to the photo-
t
tration of ions llnd free electrons (n "rod II b ultraviolet and x-radiation from
I t ic effect in atoms and molecule!! p UC(!( Y I
"
the"sun. Some 0r t',e reactions that occur lIlorc frequcnt y are
The atomic oxgell producOO combincs with molecular oxygen to form Ozone, 0 ,
3
which ill turn undergoes photochemictil diSSOCiation by absorption of ultraviolet
XO + }/lI ...... :\0+ + C- (.'i.3 cV),
radiation of wnvc!cngth between 2-100 A and 3600 A (that is, photons of energy X2 + h" ...... :\t + e- (7,4 cV),
betwccn 5.2 eV find 3.-1 eV). The reaction is O 2 + hI! -> ot + C- (5. 1 eV),
He + }/lI-.lle++ e- (:N.6eV).

. . . ed' rcnthcscs. r.lany olher secondary

These two reactions absorb ultraviolet radiation so strongly that they remOve prac-
tically all the ultraviolet radiation coming from the SUIl before it reaches the
earth'l:! surfnce. If this ultraviolet radiation were nble to reach the earth's surface,
it would dc;;tl"(!y mnny organisms by means of photochemical reflctions with cell
componcnt~, cnzymes, etc.
The ionization polel.lllais are IIld~::c. asl~ ::':ult of these ionizations. .
reactions take p.lac~ lI\ the atmosp f hotoionization is radialit't capture. 1n radla-
A process whIch IS the reve~ o. P . F 's captut(!(i into a bound state
live ca])ture, a free electron With klllctlC C:I:rgy. "k I
by an ion with the cmission of a photon. I hat IS,

T he photogt'llphic proCCllS il:! still another cxample of a photochemical reaction. A ++e--. A + It~.
Undcr the aetioll of mdiation, moleculcs of silver bromide undel'go decomposition,
The cllergy of lhc photon is
with the s ilve!" aloms fOfming n so-called latent image OIL a sclLsitized film. Latcr,
in the devc!opillg ]J1'OCc;;!J, the film is treated in such a way that a permllnent imllge
is fOfmed. hI! = E t + I. (1..11 )

WhelL the photon has cnough energy, its absorption by an atOIll o r a molecule When the energy of a photon .IS muc Ilarge I r than the binding energyI IIof that
1 __ ,.",'"Iered as free.
the
lIlay rc:;ulL ill thc I'jection of an clectron. What is left is an ioni7.cd Iltom or mol- . ! Ie the electron can u<:
eleetroll J1\ an atom or 1110 eeu. ' _. I able process than the photo-
case Compton scattering (SectlOIl 1,;,) IS a morc pro)
 32 The jQmrdolioru of quanfum phy&ia
(1.9
,
1.10) PUl'lick, Ulld fltld, 33
, thickness :z; of the substancc is given by
1 = l oe-:!z, ( 1..t3)
where ~ (expressed in meters-I if:z; is expressed in meters) is a quantity character
istic of each substance and of each proccss; it is called the coefficient of linear ab--
IWrplion or the macro&copic crQ.S3lCclion. It is a functiOll of the energy of the photons
(for the dcrivation of Eq. 1.43, sec E.ICample 8.8).
For cach substance, there ill one macroscopic cross section for each possible

---
\ --_..!~(Pb)
\
\
\
- .............. \
-\.
,...... ..."
,--
proccss, such as photoelectric elTect, Compton scattering, pair production, etc.
The total cross section of a substance is the Slim of all partial cross sections. Fig
(Ar)--+-
/I Al \...... / ure 1- 19 shows the individual and total macroscopic cross sections for aluminum
\ \ ... , /Irr (1)0) and lead (or the three processes mentioned. Note tha~ at low energy the photo--
\ \ ...... , /
\ '- / .......... electric elTect is the most important, at medium energies the Compton elTect
\ \ / ......... dominatcs, and at high energies pair production is the main l)toecss.
J {AJ)\ \ I .........
\ X............... :.-- 1.10 ,-",.tides 1111,1 Flt! "/~
" I \ ... .... ... - ...... ,
I \ ,>0'
\ : \ ,,: '" Another important revolution in physical concepts took place at the end of the
'~"------<i'r-''------;--c'
10- ro - __-"'~'('~~~'~'~'A~I~)_'~'~"cJ
...
first quarter of this century, and radically changed our approach to the description
! JU 2 of motion of a partiele.
PhotQn energy, ~rc\' !O
Our scnsory experience tells us that the objects we touch and sec have a well
Fig. 1-19. Macroscopic cross l!eC(lOIlS ( th defined shal)C and size and therefore are localized in space. We thus tend to e.... trap--
lead, The IIOlid CUf\'(!3 lire the tOlar or .e absorption of photons in aluminum , olate and think of the fundamental partides (i.e., electrons, protons, neutrons, etc.)
e lOllS oe to t hc Ilhotoelcclric ctre.::~'
lie( d eroS!!
th I L ' Those Ia belA..I
tle<:trOllll "U
, are the llartial cross
'"'
as having shape and size, and so we tend to imagine them as being somewhat like
the Cam IlIon effect those labeled III ' OSC. ll,,,,,led lJ are partial Cross sectiolls du, I.
are partlll cross sect'Ions d ue to jllllT
. production. small spheres, with a characteristic radius, as well as mass and charge, This, how
elcctrlc effect. I r the ellergy of the ph t . J ever, is an e ... trapolation beyond our direct scnsory experience and we must analyze
is twice the rest energy of the clcct 0 Jon IS urger than 2m.,c2 (= 1.02 :'lIe", which it carefully before we accept it.
lion of an elcctron-positron n"ir (T"'h" , y~t an~thcr Process may OCCur: the cren. Experiments have shown that our eICtrapolaled sensory I)icture of the basic con
, , ,- , e POSitron 15 a parCel I ' I stituen(.s of matter is erroneous. Tho dynamical behavior of elementary particles
a$ lie e eclron, but positive charg ) Th ' I e lavmg t Ie same mass
called pair production, may be writ:~n as e creation of nn clcclronpositroll pair, requires that we associate with cach particle a field-a maller fidd-in the same
way that, in the reverse manner, we associate a photon (which is equivalent to a
"" -- e+ + e-, partidc) Wilh an electromagnetic field. This matter ficld describes the dynamical
' , (1.42) condition of a partido in the same sensc that. the electromagnetic field corresponds
T' liS procC&! WIll bc discussed in tl t '" See' to photons which have precise momentum and energy. In discussing the connec
that it cOllsists in the tnulsformat,e al fm , fLon 9,3, At prcs('nt, let US say ollly tion betwccn the matter field and the dynamical properties of the particle (i.e. ,
Smce t,Ie energy associated with " Ion 0 a ploton intoalr C"ec ron p , us a POsitron momentum and energy), we may be guided by the relations previously found for
J " Ie rest mass of all elect ' '
t Ie mrn!l~\Um ellergy of the photon needed t ron or II. posltr~1\ is moe 2 , the photon. Writing thc relations ( 1. 28) in reverse, we may assume that the wave--
must obVIOusly be 2moc~, a produec an electronposltron pair length X and the frequency I' of thc monoc hromatic field associated with a particle
At high energy, clccU'om:lgnetic l"ad' t' . of momentum p and energy t: are given by
either raising the!)) to an excited stat I~ 101.1 may also Interact wilh atomic nuclei
in a so-<-aJ!cd fllwtonuclear reaction c, eJectm g a nUc/Cftr part ic/e (~uch as a prolon) h
X =- , (1.44)
' or even brca king tli" ,
nuc ,car processes will be discU"'~A' " Ch " nul' eus apart. These p
, ""'-.... HI apter 8.
Yhen a beam of radial iOIl passes throu h matte r . , where h, as before, is Planck's constant. These relations werc first proposed ill 1921
by the va~io~$ processes we have mcntio~led. Th , Its ?lIergy 1$ gra~UAlly ~bsorbed by the French physicist Louis de Broglie ( 1892- ), and for ihat reason X = hlp
of Ihe radlatlOlI /)cfore it entcl'l!: the s b t ,~, glv.en that I 0 I.~ the lIlten.:;ity is sometimes called the de Broglie 1.I.'at'elerlgIJi of a particle. Introducing the wave
u S tUlce, Its lIilell.Slty after it has traversed II
number k = 21fI X and the angular frequency w = 211"1', we may write the rela
 34 Tht Jowl/Julio/!& of qu.ell//um physict
(/.10 1.10) P(Vlidu (J1Id fitbb 35
{iolls (1..1-1) in the more symmetric (onn

'7T =..h ,.. h

t" 2".' E = -;;--
_T
W,

or, defining a lIew constant designAted by hand ealll)(l/r-oor,

II. = J'l!.". = 1.0541 X lO-lt J s,

we have
p = Id.;, b' = II.w.
Fig. 1-21. Diffraction of clcctrons
H our Assumption, o..s expressed by Eqs. 0..14) or (1.45), is correct, we may CXI)cct by crystal powder (courtesy of Dr.
IhaL whenever the motion of a particle is disturbed in such a way that the field Lestcr Germer).
associated with it can not propagate freely, interference and diffraction I)hcnomcnll
should be observed, as is the case for elastic And elcctromagnetic wavcs. Tllj>:! is
indeed what happens.

Fig. 1-20. Experim('ulal arrangCtl1CrH . . . . G P Th mson (1892- ) began a series of

for observing electron diffme!ioll through In l\)27 the Bntlsh SCientist '. . I 0 MM e of 0. beam of electrons through
crystalline material. experiment.<! whose PUTI>O!!e was t o st~dy ~ Ie ~~ectr!lS ,w.ssOO through the film, they
a thin film of crystalline material. A tc~ t I,C,. I 20 If the electrons had behaved
1 l t a s shownm'lg.-_. _-'
struck a phot-ograp IIC pac, . It blurred image would have been observ .'u
as particles in the macroscopIc !!ensc,. I a difTerent scattcring by the
because each electron would undergo, ": ge~I~~l~ was identical to the Debye-
~
Incident
beam or
atoms in the crystal. Howe~cr, tl.le
Scherrer patterns for x..~ray dlfTrac~IO~\
u
r:f,
: ~I crystalline substance, as indicated
\~'h~l an electron beam passes through
eJ~1'OIllJ in the photograph of 1lg..1-2 1. SIIIlI!ar) ~atlerns (also observed with x-rays) as
Il. single crystal, One obtall~. Laue~I>O~.. 1 the structure of these p3.ltems olle
seen in the photogmph of hg. 1- __. rom

Before we discuss the experimellts that reveal interference and diffraction of the
maHer field, let WJ Iry to estimate the value of the de Broglie wavelength). asso-
ciated with n particle. Electrons aecc[cmtec! b.r an electric pOtcnlial I' gain an
energy cl'; hence their kinetic energy is p2/2m~ = e lf so thaL p = 2m~.
Therefore, introducing the values of e, me, and h, we obtain the dc Broglie wavc.
length of such electrons

(lAG)
wllere r i~ exprcs.~ed in volts. This for/llula can also be used whcn the kinetic
Fig. \-22. Diffr3.c\ion of SO:kV
clectrons by II. singlc carbon \)!;rllph~ Ie)
enel'gy of the electrOIl is exprc;;.sec/ in clectl'Oll volts. For I' ..... IO~ V (which is in crystal (courtesy of R. ~~eld enl'elch,
thc rango of voltage used in TV tubcs), the wavelength is aoout 10-11 m, eoOl_ Uell Tclephone LlIhorIl.IOTlcs).
l>umble to thf;l wavelength of x-rays. This means that if we send a beam of frust
clecl rons through a crystal, we s hould obtain diffmclioll paUefils which resulL from
scattering of the matter field. These diffraelion I>uUerns, corresponding to the in-
coming electrons, shOUld bc 8imilar to those obserVed for X-rays.
 --------------/~,. ....................--
36 Tk /Owl(ialiolll oj quantum phYfia
(/.10
I
1.10) Parlic~1 and fu:1d8 37

have a wide spectrum of energy (in other words, they vary widely in momentum),
or, which is equivalent., the neutron beam is not monochromatic; rather it eontaill8
a spectrum composed of many de Broglie wavelengths. When the neutron beam
, from the reactor falls on a crystal, of LiI" for example, the neutrons observed ill
,/f the symmetric direction correspond only to the wavelength" given by Bragg's

,,, \\,, oondition (1.47). Therefore they have &. welldefined energy and momentum. The
crystal then acts as an elltrgy filttr or monochromator. The monoenergetic neutron
beam is in tum used to study other matcrials, by diffraction, or to analyze nuclear
reactions involving neutrons of definitc encrgy.
f.' ig. 1- 23.
electrons. Davi&'lOll and Germer arran"m,"' (or ob.servin, n.r gg SCII.I tcring of EXAMPLE 1 .8. What is the de Broglie wavelength or thermal neutrons at a tempera-
ture of 2501
carl cOIllJlute the de Broglie wavelen th >.. if Solutio'!' By fhermal nell/rona we mean neutrons which arc in thermal equilibrium with
crystal plnncs and if one applies the g~ I on~ knows the spacing betwC<!n the matter at a gi\ell temperature. Thus the neutrons have an average kinetic energy identi
The resulting values of >.. can b O~,U ~ t Il.L have bccn derived for x-my, cal to that of the molecules of an ideal gas at the II/une temperature. Therefore the average
1'1 " c compn",u 1I'1lh those bt' I f
Ie resu t IS complete agreement, within til r ' 0 am,C< rom Eq. ( l AG), kinetic energy of thermal neutrons i~ E _ ikT, .... here T is the absolute tempe rature
In the cclcbmtcd experiments be D . e lIn1ts of cxl>cflmcntnl error. and k is Boltzmann's constant (sce Eq. ]0.41). Given that the temperature is 250, we
thc same time a!J those of 1'1, Y). ,. _Il. V1SSOI1 and L. Germer (made at nl.~", have T .. 2981( and therefore E..... i!kT .. 6.17 X 10- 21 J .. 3.85 X 10- 2 eV. The
' omson, a lJ(:/l,1ll of cl t uv ...
I
tie fnce of II. crystal. The diffrn.c<-.I I cc rons was sent at. an IUl,le to corresponding momentum is "p .. ~ .. 4.55 X 10- 24 m kg 8- 1. Then, using
. I .... e ec{rolls wurc obsc ..1 b
'(1
Eq. (1.44), we find that the average de Broglie wavelength of the thermal neutrons is
. r~e\J. ~ mcans of a detector
symrnctnCfl Iy located, 1\8 indicated in Fi g _

registered by the detcctor was a maximu

;t
nUl~cmcllt for observing x-my diffraction 2~. TillS IS similar to the Bragg lIr.
\\~ found that the elcctron current
" .. 1.85 X 10 - 10 m. (Incidcntally, noting that the SC]Jaration of the planes in a NaCI
crystal is d .. 2.82 X 10- 10 m, we see that the first diffraction maximum for neutrons
of this wavelength occur!! at an angle (J .. 19-.)
for xrays, was fulfilled. The Bmgg 00 dm,~ve,?, tune thc Bragg condition, derived
n I Ion IS expressed by.
EXAM/'Lt: 1.9 . .-\n electron is rele&;JC(1 at a Kreat distance from a prown. Find the
2d sin 9 = 1/>', wa"elength of the electfon when it is (a) 1 m from the proton, (b) 0.5 X 10 - 10 m from
. ( IAry the proton (this distance is of the order of magnitude of the radius of the orbit of an
where d IS the separation of s ucc iv . ei('ctron in the ground sl.lI.te of a hydrogen awm).
by Efl. (lAO). CSS c atomiC layers in the crystal, nnd >, is given
So/J,tio'I ' The potential through which the electron h&4 mo\ed, when it is at a distance r
(ram the proton, is

I' _ ~/4rfOT .. 1.44 X 10-'Ir Y,

Fig. 1-2 1. Neutron crystal spectrometer. where r i.s in meter;!. Sub.~tituting this value into Eq. ( 1.46), we find that the wavelength
of the electron is

>, - 3.24 X lO - s v'T rn.

From this result we note thllt the wavelcngth decreaI!C8 as the electron approaches the
?hc samc I>hcnomcnon of Bragg diffraction h IlrotOIl. The reason for this is that the electron i9 accelerated WWllrd the proton, Ilnd its
with protons and ncutron, ", [ I.. . .as bccn observed in expcriments momentum increases M the distance decreases. Whcn the elcetron is 1 m from the prawn,
f [I . " u roll {I mclton IS es . II .
o IC most Powerful mea ns f t d . pccw. y IIscful, slIlce it is one the wavelength is 3.2-1 X 10- 6 m. When the electron ill 0.5 X 10- 10 III from the proton
monoenergetic beams of "''',::. S udYlIlg ,crystal structure. Experimcnters U~ft the wavelength i~ 2.27 X 10- 10 III. Thia wavelength is of thc order of magnitude of the
'rl ' .... vllS an nna yze tI . ""
IC neutrons emer,;"g f~,. I lelr passage through the cry"" dimensions of the hydrogen alom. However, to accommodate the eletlron in a stable
' v ,1 a nuc ear reactor th h .
roug a porthole (sec Fig. 1-24) orbit around the proton, in R hydrogen atom, it is ncceSJlllry to adjust it.s wavelength to
an appropriate value (which is approximately 3.]4 X 10 - 10 m). This requires, as will
See, for example, FUndam.ental UnitcraitIJ Phyaica Vol" II o . be seen lster, the loss of s certain amount of energy by Ole electron, which is emitted as
, ... me, QCcIJon 23.8.
radiation.
 38
--------------~
TIuJ JoulldaliO/~ of quanlum phnir&
I
.......--......--....---
I

(1. 11 1.t2) 39

"-ig. 1-23.
~---------~----------~
Continuous wave train oorresPOllding LO an unloeatized par lieJe,
Fig. 1-26. Wave packet corresponding t.o a particle 1000Jized ""ithin the distance 4%.
1.11 '"rti,I"N IIRfl " ',"", ,-",.h,.,.
of thc particle. We conclude then that a particlc localized in a certain region of
USin,g relations (1.4,1), we may represent the field cor .
movlIlg wilh II well-defined momentum p d "'"J>ondl,n g to II free r>a rticle space is associated with a ficld or wave packet whOSe amplitude is important only
r all energy ~ = 1) /?II b
wave 0 constant flm plitude, us s hown in Fi g 1-25 S
J
- Y 0. lUrmOlllC
in that region; the velocity of the ]>articlc is the gro ul) velocity of the field Of wave
amplitude of the wa ve be the san" h ," ymmcl ry demands Lha~ the packet.
. 10 Iroug out II I Space since "
actmg on the particle that could d"" ' (' . ' lore arc 110 forces
. f IS or
rcglonso spaccthnll in oth ers. Thc pha l"t f'
le associated matter fi Id .
C 1ll0rCII1SOlllC
se vo DCI yo t le field of the frcc particle is
1. 12 lIelsen berg's I)nt*-rtaln t " 'rlnclple lor
Position and lflomentum
v" = ),/1 = p!!. -hE = .
'P
= L - I
2m - v. Now we encounter a special situation which cannot be explained ill terms of classiCllI
mechanics. For a wave packet to be localized in space, it is necessary to superpose
~!a~1~8, C~::C~i~l~~t:~J:I~Y o~~~~~cm~tlcr i~
field one-half the particle vclocity. Th is
several fields of different wavelengths " (or with different values of the wave num

7
velocity of a ])Ure hannon~'ave (Iin:;;eve;v SlIlce 1 CIlnllot IllC/lSUre lhe phase
ber k). If lhewave packet extends over a region IU, the values of the wave numbers
of the interfering waves which compose the wave packet and have an appreciable
of the waves. (See Appendix III ) Th/fa e can on y m~ure the group velocity amplitude fall within a range 4k such that, according to the theory of Fourier
is the same throug hout all spa~ Sll . ~ ct,tha ththe am ])lltude or the maHer field analysis,
'.
d oes 110t give ggCil..." t lat t e maller field of a r .
lIlformation aboul the I""", . . ree particle ru:4k .... 2....
d fi cd "'"" Izaiion III space of a free pa f I f
e III momelltum. 111 other word.s the It fi Id' . d r IC e 0 well
of the particle, Ilnd an obscn.ation ~f th m~ I~r be IS 1I1 ependent of the position But, according to Eqs. (1.44) or (I.45), different wavelengths" or wave numbers
the positiOn of the particle. C I" Y SOme method would lIot reveal k mean that there are several values of p. such that !J.p == h !J.k. Therefore, when
we recall that h = 211"", the above expression becomes
From our physical intuition and our knowled f fi I
a particle lOCalized within a certain region ~ r'e 0 ehds and wavc:;, We know that lU!J.p _ h. (1.48)
field Il'hose amplitude or intensity is la r .x 0 h space~ ould correspond to a matter
A field may be built up in a ccrt ' ge.1I1 t a~ region and very small outside it. The physical meaning of relation (1.48) is as follows: If a particle is within the
thro ugh the process of int erferenc"albn region an. attenuated out.side tha t region region % - t 4% and x + ! lJ.l: (that is, !J.x is the uncertainty in the position of the
, ", y superposmg waves "... f d. f . particle), it.s associated field is represented by Superl>osing waves of momenta be-
all( wavelengths T he rcs It . I erent rcquenCIC$
wit h which the \~Ilve ')fLCk~' ,,'ro",1l"aL,"e !!~Cke,l, as shown in Fig. /- 26. The velocity tween p - ;!J.p and p + t !J.p, where !J.p is related to lJ.l: by relation (l.48). We
Jaga es IS t Ie gro up vcloc't ,. ,. . my that !J.p is the uncertainty in the momentum of thc particle. Relation (1.48)
v~ = dw/dk (sec Ec, \ ") U ,. _ I Y I'~, W llC I IS given U"
. t . ; I . smg J"callons(J'/')a II' 2; 0 implies that the larger ~x is, the smaller!J.p is, and conversely. In other words,
write rhc groul) velocity of the matt f Id .' iJ n.< ~ = 11 2111, WC 111i1)' "tc-
er Ie cOrlesl>ondmg to a free pal"liele Zl.S infonnation about the localization of a particle in BI>ace is obtained at the expense
v~ = dJ~'/dfl = fI/ m = v. of knowledge about it.s momentum. The more precise our knowledge of the posi-
tion of the particle, the more imprecise is our information about it.s momentum,
T hus, just as our physical iUlUition tcll '1. I II and conversely. This is why a particle of well-known momentum (~p = 0) is
matter field (i.e., the velocitv of proJlag:t~ I :,I~U < bc, lh~ gruu]) velocity of ihc represented by a wave of constant am pl itude extending over all space (lJ.l: _ >Xl),
. IOn 0 e pac kct) IS cqUa.llo the velocity
80 that our knowledge of the position is nil. We cannot accurately determine both
 The /otllldaliOlu 0/ quantum physics

y
(1.12 1.12) fltutttbu<il wlctrillillly principle

illustrate, let us consider some siml)le experiments. Suppose, for c.xample, that
"
I
___________~~~f~
we want. to determine the z-coordinate of a particle by observing whether or not
the particle passc.5 through a hole (of width b) in a screen (Fig. 1- 27). The precision
with which we know the position of the particle is limited by the size of the hole;
that is, 4.J::: ...., b. But the hole disturb.!! the field associated with the particle, and
this results in a corresponding change in the molion of the particle, as seen by the
, ~------~~-------x diffraction pattern produced. The ullc('rtainty in the particle's momcntum parallel
" to the X~a."is is determined by the angle 6, corresponding to the central maximum
,,"",, of the diffraction pattern, since the particle, after lravcrsing the slit, is most prob-
ably moving within the angle 28. According to the theory of the diffraction pro-
--: t..--:l4
, '' duce<1 by a rectangular slit, the angle 6 is given by sin 8 = Vb. Theil

,,, ',, 4.]) _ p sin 8 = (h/"H" l b) = h/ b

, ,,
p ,,, ,
,,
is the uncertainty in the momentum parallel to the X-axis. Therefore 4.x!J.p ... 11,

,,,
in agreement. with relation ( 1.48). Note that. to improve our ability to determine
,, t.he exact. positiol1 of the particle, we must usc a very nal'row slit. Buta very narrow
, ,, slit produces a very wide central maximum ill the diffraction pattern, which means
a largc uncertainty in our knowledge of the X-component of the momentum of the
particle. Conversely, in order to reduce the unccl"tainty in Ollr knowledge of the
F i g. 1-21. Measurement of position and momentum of a particle Ilassing through a slit. X--component. of the momentum, the central maximum in the diffraction pallen!
must be very naITOW. This requires a very wide slit which, in turn, results in a
the llOSitioli and the momentum of a particle simultaneously &0 that t.x = 0 and large uncertainly in the X-coordinate of the particle.
Ap =. 0 at. the ~me timc. Such knowledge docs 1101. confonn to relation (1.48).
n elatlo~I .( 1.48) gives the optimum relation among the unccrtainties t.x and A,} in
the position x ~nd the momentum p of the particle. Howcvcr, in most cases x and
p are known with I~ accuracy, so that we must write instead of relation (1.48) the
more general expression
"-ig. )- 28. )Ieasuremcnt of position and mo-
mentum of s Imrticlc by mcan~ of II. microscol)(' .
.u4.p ~ h.

'~he result expressed by relalion ( 104.8) is called Hewmberg'. I.mcerlai1lly 1)rillciple

which lIIay be stated in words as follows: '

1/ i.s. irlllW8.ibie to /mow 'imulwJUously and wi/h, U(M;/neu both the [nddenl
po,flllOn and Ihe momentum oj (l partide. li~ht

This prinriple eXI)r~ one of the fundamental facts of nature, and to a ccrtain
extent may be cOll.':lIClercd as more fundamental than relations ( 1.4!i), although
he.re we l~av~ proceeded in the opposite manner. To better understand t.he unee ....
talll!.y prlllciple, let us considcr some possible physical situations.
To say ~hat. a particle is at point z with momentum p means that we have to
meaaure 'lmullaneously the coordinate :.t" and the momentum p since without
measuremen~ we do not have information. But if we analyze the 'ProcCl!8 of rnea~
surement we note t1~t on the ato~ic seale we cannot measure either the po~ition
or the momentum Without apl>TCClably disturbing the motion of the particle. T o
Another experiment. which indicates the impossibility of observing a particle
without disturbing it is the case in which we tI-y to determine the position of an
electron by mcans of a microscope (Fig. [- 28). To observe the electron we must
illuminntc it with light of some wavelength X. The light thnt passes through the
mieroscope is that which has been scat.lered by the electron under observation.
The momentum of the scattered photons is Pl'ltolon = lilX, and to penetrate into
the objective, the photons must move with ill the cone of angle a, SO that the
 \
Th~ foundalioru of qu.anil4m ph;ysia
(1.12
1./3) TIl~ u/rctrlainl;y nlalioo jor li~ (lnd entI"!J;y
X-coml>OlIent of their momenta has an uncertainty
,. I
IIp - p"bol.On sin Q' .... IId/2"AY,

~
since sin Q' .... d/2y. This is also the uncertainty in the X-componellt of the electron
iII0melltum afte r the scattcring of light, since in the scattering process some momen_ (.I, (I)
tum is exchanged betwccn the electron and the photon. On the other hand, the V
exact position of the electron is uncertain because of the diffraction of light whcn
1/
it ]>aSSeS through the objectivc of the microscope. The uncertainty in the position
of the electron is thus C<lual to the dia rl1eter of the central disk ill the diffraction
patten!. This diameter is given by 2y sin 8, with sin 8 .... "A/d. Hence
--d------<
o
.d% .... 2y sin (J .... 2y"A/d.

Therefore again lu: IIp .... Ir. Kote that to improve the accuracy of our knowledge
of the position of the electron 11"0 must usc a radiation of very small wavelength,
but which produces a large disturba nce in the momentum. Conversely, in order
to produce a small disturbance in the momentum, we mu.st use radiation of very
long wavelength, which in turn gives rise to a grea t uncertainty in the position.
T hese two exa mples clearly s how that the unccrtainty prinCi l)le is a direct con_
sC<luellee of the process of measurement. AL the atomic level , measurement in-
evitably introduces a significant perturbation in the system, due to tho interaction
betwccn the measuring device and the mea.surcd quantity.
The uncertainty principle implies that we can never dcfine the path of a particle
with the absol ute precision Ix>st ulatcd in classical mechanics. Classical mechanics
still holds true for large bodics, s uch as those of usual concern to the engineer,
because the uncertainty implied by relation (1..18) is mUeh smnller for a mncro-
scopic body than the experimental errors in the measured values of x and p for the
body, due to the smallness of Planck's constant It. However, jor particle8 oj aiomic
dime n8iol/s, tile con.cept oj trajectory hM 110 meaning, since it CalI/lOt be defined pre-
cisely; thcrefore a picture of the motiOIl different from that of classical physics is
fC<luired. For the same reason, concepts s uch as velocity, aceelerntioli, and force
arc of limitc<[usc in quantum mechanics. On the other hand, the concept of energy
fS of primary importance, since iL is related more to the "statc~ of the system than
to its "[)ath," as we shall sec in the nc.1Ct chapter.
To describe the dynamical 8tate of 8 particle in a graphical way (i.e., its position
and momentum at each lime), we usc a representative spa~, called plrau space.
For thc ease of one-dimensional motion, the phase space hllJ! two dimensions, with
the abscissa corresponding to the positional coordinate x and the ordinate to the
momentum 1) (Fig. 1- 29). In classical mechanics the state of a l)Article is repro-
scntc<[ in phasc space by a point with coord inates (x, p), since in classical mechanics
we can accu rately detennine both position and momentum !:limullaneously. As the
particle moves, t he representative ])Oint describes a line ill phase space ( Fig. 1- 298).
We have disregarded the factor 1.22 which appears in the theory of diffraction or a plane
wave by a circular aperture.
(~) Ib)
Fig. 1-29. Clnssical and qU!l.ntal p!l.lh of !I. p!I.Tlic1e in phase SJIIlCll.
In qua ntum lllechaHics the picture is different. Let us divide the pha.'le space into
ccils, each ceil having sides Ilx and IIp so that lu:.t:.Jl = Jr. T he~ th~ mos.t. \~'e call
say is that at each momcnt the representative pOlllt of the parlt~le Ires wlt~m.onc
I II A, l ime goes on the path of the representative POUlt falls wlthlll a
8\lC1CC. , . ( f" l 29b)
ribbonlike path fonned by p8lchillg together a scnes of 'ils sec ' Ig. - _ .
1. 1:1 Th,. I : n,','rt,sintll n,./fltion for Tim,' fin,' linf'rYII "'
In addition to the unccrtainty relation l!.x Ap .... Ir bet\\:ccfl a ooordir.late and ~he
corrcsl}()IIding momentum of II. moving particle, there IS an uncertamty relatIon
bet.ween time and ellergy. Sup])Ose that we wa~lt to meas ure 1I0t ollly the ellerg~
of a partide but also the time at which the partrcle has such ene~gy. If:-l and Il
a r-c t he unccrtainties in ihe valuC.'l of these quantities, the followmg relation holds :
(1.49)
We can under.;t!uJd this relation in the following way. If we want to define the
time at which a particle passes through a given l)Oint w~ must represent ~he pa~~
tide by a pulse or wave l>acket having a very short durnlton Ill. But t~ bUlI~ s ue
a pulse it is necessary to superpose fields which have different frequcncles, with an
amplitude appreciable only in a frequency rallge ~w ccntc~ around lhe frc<luency
wand such that, according to the theory of Founcr analysl'S,
l!.tllw _ 211".
l\ f ultiplying by Ii and recalling from Eq. ( I.y.) that B ~ II.w and ~hat 27rh = h,
wc obtnin relation (1.49). f!elntion (1.49) gives the o])tlrnuUl relal!on ~mong the
uncertainties t:.l :md 1lE. Howevcr, in most eases, t and B arc known WIth less ~c
curacy, so that wc must write instead of relation ( 1.49) the more general expreSSIOll
III t:.E ;:. I,.

4ft Th~ jOlillJO/iolll of qll/Irl/um ph.v.in
The untenninty . ~elntion {I. I!) ~Iuires th.at we revise om concept of s tat ionary
states. Let us con",d:r lUI elcclron III an CXClted stationary statc in nn MOlll. The
electron after a certam time will>;uIT('r a radiative transition into anOlh('r station.
aQ',stale of less energy., 1I 0we~er: we have ~10 means of I)redicting with eertaillty
I~o\\ long li~e eleclron.\\'lll rcmal11 111 the sltltJol1ary state before making the tmllsi.
llo.n: As \\'111 ~)e ~n 111 the Il('Xl ehal)tcr, the most we can talk abom is the prob-
~bllllY per,ullIt tllue lhaL th~ clf:'Ctron will jUl.lll~ imo a lower encrgy state, There-.
ore t!le .Il\emge length of tlm(' the electron IS III the stationary .. talc, also ealled
the 111~I~m~ of the state, and which is invcr.sely proportional to the tran~it ion
probabIlity we ha~e mentioned, i~ known within an uncertainty t11. H ence the
energy ?f the ~.tatl0nary stille ()f the electron is not known Jlreci:;;cly but hIlS un
ullcerl1\11~ty J.j.., s uch thaI n:lution ( lAD) holds. Often 118 is d c.;igna ted ns the
energy twllil of the ~tatc whose energy is most I)robably betwccn F - t ' "
F + I 1''' , I ~ ... . ane
.' . ~ ~ ( I' Ig. 1-.30). \\ c may a ....~ll!lle that III is of the order of Illllgnil ude of the
I1fetlllle of the c1't:eite<i ~'iIte. Thu~, the ;:horter the lifetime of an {xeited state the
l~rg~r th.e ~n~e~tuillty in the energy of the state. For the ground st !\le, lI"hosC
Ilfeur~l? l ~ ill/illIte hecause a system which is at its ground " tate CIlJ1noL suffer Il
Ill" _ 0 to a stil tionury stule (,f lower cne""'y
tran:\Il!On '0'
we have Ill ..... (J)_. '1'1'
1111 ~Ie(.s
- and the energy of the gn)unu state can be deter!l1irl{'d accumtcly.
i~
!~o E1 ...- -- __ .,-I____. .
Exdted SlMe
1 El-El+~E
.J-El
E2-Er-~E
E, _ _ _~LlLl----
Ground s\.:,te
Fig, 1-30. \\'idth of energy
Beea~ISC of th~ ~r\{'r~y widlll of .~latiumu'Y states, the energy J'elca~ed or ab.
sorbed III fl tt'llllsltion 1~ llot well defined. Thus in a trflnsiLioli bet.wccn I'latcs f
cnergy H t fintl 1~'2' the pllOt/,n" ('lniUed or ubsorbed fall in the cnergy r'.Inge
0 t-flinty due to the finite life of all e.xcitcd nuclear state is much le!!ll than the recoil energy
1:'2 11\ } J./~.
where !J.J~' il'l tire 1('1111 en('rg)' Ililhh (If both states.
,
1.13) T M Uttur/ainty re/a/ion jlJl' li1Jlf! and tlltrgy
( 1.13
A further broadening of the encrgy of the sta.tionary states is caused by the
electromagnetic Doppler shifL The atoms of a substance are in motion, some
advancillg toward and some retrc&ting from the obsen'er, and the observed fre-
quency of the radiation emitted by the atom dilTers aCCQrding to the direclioll of
relative motion. In most atomic and molecular transitions, the broadening due
to the Doppler effect is much greater than the broadelling due to the uncertainty
principle, but is usually smaller fo r lIuc1car trBlisitiolis.
EX,.jMPI.E 1.10, The JXlI!8ibility of resollllncc absorption in alomic and nuclea r transi-
tions as a result of the energy width of the stationary states.
$o"a iOlI; In Example 1.6 we saw that in II transition ootwecn ijlate~ of energies E', and
/0.'2, the photon emitted or absorbed has an energy which is smaller or Inrger, re~Jlectively,
I thall B2 - Bl by an amount ( f:2 - El)2 / 2Mc 2. Therefore, if the energy width 6 is
larger than ( E2 - f:I )2/2Mc 2, pholOns emitted by one system call be absorbed by an
other of the same kind; but if All is smlltter, the absorption docs Ilot necessarily occur.
The first situation i~ normally found in atomic and molecular systcms and the second is
more common in nuclei. For example, in the atomic case of the 4.86eV transition in
mercury, mentioned in Section 1.8, the lifetime of the excited state of mercury is about
'II
10- 8 s. A mercury atom, wh054l alOmic mass is about 200 11.111U or 3.34 X 10- 25 kg, has
a rest energy Mc 2 _ L86 X 1011 eV, Therefore the tern) accounting for the atomic
recoil with C2 - EI - ....86eV is
The uncertainty in the energy of the mercury &tom excited le\'el, which has a lifetime
III _ to- 8 s, is llE _ h/ Ill _ .... \4 X 10 - 7 eV, This i~ much lurger than the correction
term, by a faclar of about tO~ . From this typical example we may IhlUl conclude that
recoil effects due la momentum conscrvation in atomic and molecular transitions do not
hinder resonance absorption.
Ail an example of a nuclear tran~ilion, consider lhe ease of the 1.33 :\leV gamma ray
emitted by lIoNi, A nickel :l.tolil , whose atomie ma.ss is about 00 amu or I X 1O-2~ kg,
hB.!! a rest energy Me 2 _ 5.61 X lO,oeV. Also f:2 - f.1 - 1.33 X 10'eV. Therefore
the correction tcrm which accounts for the nuclear recoil is ( E2 - E,)~/ 2M e2 - 15.8 eV,
which is relatively larger (comlmred with 1~2 - E I) thsn in lhe atomic case. The life-
tinfe of the nuclear excited st.&te is III - lO -u I. II ellce the uncertainty in the energy
of the excited leve! is ilK ..... hlAt - 0.414 eV, which is 'm oiler lhan the correction term
by a factor of about 38, Thcrcfore recoil effects due to momentum con!!erv!Ltion in nuclear
transitions are important. These effects make it impoSllible, in many cascs, for II. nucleus
te\'cl~.
to absorb the gamma photon cmitted by a110ther simihr nu cleu,~.
EX ,.IM I>'.E 1.11 . Discussion of the i\I6Sl1baucr cffect.
$01111,;0,,; In the previous e~amplc we I$3W that in nuclear tran~itio11s the energy uncer-
of the nucleus, thereby making it irnpo5.'!ible for II. )'-ray photon emitted by a nucleus to
00 absorbed by another identical nucleus. I! o"'e\'er, under special circumstlmces, recoil
elTects can be reduced by a large factor. This is pOilSible when the emitting and absorbing
 The /oundaiw 0/ quanlum phy,ia Probftrru
(1.13

n uel~i a.re bound in a crys t.allattice and the conditio

recoils, Instead of just a si ngle atom ,,~,. Th Mh are such that the wholc crystal
. ~~.mg. enlemassiseol Ihlh .
energy IS very 8mall compared with E _ E Th arge. a t e reCOil
1. ~Early Work in Electron Diffraetion,~ G. Thomson, Am. J. Plly,. 29, 821 ( 1001)
!"elIulting in the ~called M~abautl' tff~' h.1h us resonance absorption may occur,
by the German physicist R. L. M6ssbaue;. w IC was observed for the firs~ time in 1958 2. " The Scattcringof X-rays &II Particles," A. Coml)ton, Am. J. Plly,. 29, 817 {1961}
3. " Einstein's Proposal of the Photon Concept: A. Arons and :\1. Pcppard, 11m. J.
PhY3. 33, 361 (1965)
'~le 4. "60 Years of Quantum Physics," E. Condon , /'hl/m. TodaV, October 1962, page 37
5. " Paths to Quantum Theory lIist.orical1y Vie\\'ed ," F. lI und, Phllric. Today, August
~--/ ~Sh'ldi" 1066, page 23
6. "The MOIISbauer Effect," S. de BencdcUi, Sci. Am., April 1960, page 72

- ~~~r
A _, 7. Introduction to Modern Ph yricl, F. Iliehlmyer, K Ken nard, and T. Lauritsen. Ncw
."Ig. I- 'I.E
xptrlmental arrange- York: McG raw-Hill, 1955, Chspler 3, Sections 43, H , 4!l-55j Chapler 4; Chapter 5,
m en~ for measuring the width of an
energy level. Sections 86 and 87 i Chapter 6, Sections 00-95
S. Greot EIptrimerna in I'hyrica, Morns Shamos, editor. New York: Hol t, Rinehar t, and
Winston, 1959, Chapter 17 (Ei nstein); Appendix 2 (planck); Appendix 5 (Compton)
The M6&!ba ucr effect has been used to investi t . 9. T he f'eynmcm L-tGl!.lre~ on Phlla1c6, Volume 1, R. Feymnan, R. Leighton, and 11.'1 . SlI.nds.
tie~. For e.~ample, by means of the arrangementg:f ;;ev~~II.~ llmhortll.nt physical pro.pe r- Reading, 1I.laas.: Addison-Wesley, 19@,Cha pter37
tJf. of a nudear state can be determined \ "I' ray g . , ' t e natura! energy Width 10. Foundntiom 0/ MOlkrn Ph l/rical Science, O. Holton and D. H. D. RoUer. Reading,
ta ble whoac velocity can be
.
ad,",....
...:u.
IV'h ' h- sour~ IS mounted 011 the rim of a turn-
entesourcelsat 4 itsad" l\b.llS. : Addi$On-Wesley, 1958, Chaplers 31 and 32
, hole 111 the shielding and falls on sn aba be
tiC h' h' . r latlon passes through
material as the sourt:e. Both emitter and ~r ~ w Ie IS eompo~ of a toms of the same
a
eliminate recoil effects When the e 'tte ~r r a.e embedded III crysta!lJ to ClISt:ntially
a bsoqltion is observed: But if !.he tur;~bl: ~s a~ ~est .e~ative to the absorber, r~nanee
impo!!.Sible. This i8 duc t.o the Doppler shi:: : tl~e ~otlon re$Onant:e a~rption becomes
~uency of the cmltted "I'-ray as a
!"elIult of thc motion of the lIOurce relath'c to the ab $Or"",r. 1.4 It can be shown from Maxwell's
1.1 When an electron ie aect:lerated
through a potential difference of 1 volt equations that the electric and magnetic
I fields in a Illanc eleClromagnetic wave are
ita gain in kinetic energy is called 1 eleo-
------- --- -------_~-;.:o== tron volt (eV). (a) Sho..... tha~ leV - related by & _ dB. Show that lhe encrgy
1.602 X 10- 19 J. (b) What is the energy dcnsity in the wa\'e may be ..... ritten as
E _ foE 2 The intensity I of the wave is
increallC of an electron ..... hen i~ is accder-
ateJ through 10 V, 50 kV, and I MV? equal t.o the clle.gy flowing, Iltr unit lime,
(c) Assuming that Ihe clectron starts from acrOM a unit area llt.lltndieular to Ihe
rest, calculate the final velocity. direction of proll&galion. Show that
Fig. 1-32. Delect.or current as I _ C(o&2.
a function of the turnlable rim 1.2 A go.seous source emita JigM of ..... ave-
velocity. length 5 X 10- 7 m. Allllume that each loS The momentum density in an elec-
-8 -6 - 4 - 2 0 +2 +4 +6 +8 molecule acts as an oscillator of charge e tromagnetic wave may be written p -
~,cm.-I
and a.mplilude 10- 10 m. (a) Compute the fot X cR. Show that this expression has the
a.verage rale of energy radiation per mol- units of momentum pc. unit volume. Also
Figur.e \-32 shows the intensity of the transmitted rad' . . ecule. (b) If the total rILle of energy radi- show that for II. plane WII.Ve, B - -pc.
ab$OrptlOn occurs at zero rela tive velocit and that lall.on. Note !.hat maximum ati on of the source is I W, how many II/illl: HeMIl the reb.tion between e and cR
alive velocity increases in either di reetio:' 10' 0 I t~c absorp.tlOn decreases when 1the rcl- molecules are emitting simultaneously? in a plll.lle wave and the expression for E
sponding to a change in the Doppler fr .uen r II. t~ atlve velOCity of about 4 em 8- , corre-
1.3 E stimate the value of (dB/dO .... II.S
or a change of energy tJb' .... 1.33 X 10-~, cy 0 a?ou.t tJ~ -. "(vic) - 1.33 X 10- ",
10 givcn in Problem IA.]
given by Eq. (1.5) for a proton in a nu-
that the cnergy wid th of the Btal, ;. '00 E
..,
'''''',!
rptiOn IS prsctlca!ly negligible, indicating
u t ha &8 great. clcus. Assume zo of the order of 10- 1$ m 1.0 Electromagnetic radiation from the
and w about 5 X 10~0 Hz for low-cncrgy sun falls 011 the earth's surface :..t the rale
of 1.4 X 103 \\' m -~. A!IIlumillg that this
gamma rays.
 48 7'h~ foollda/iollt of quall/um physiet ProoltTI1.J 49

radinlion eaa be considered Mil plane wa\'e,

Are the numbers evaluated realistic? ,. . having a "-a\'elenglh of 1.25 Determine t be f rcqu ene), alld bed the
b'
estimat(' the magnitude of the el('(:trie and 1 17 fill( lall0n C , 0 wavelength of Ihe photons ab!;Or, ,;.
EXt,lain. . 10 1 A) undergoes omll 0
magnetic field amplitudes in the wave and 10- m (or , The seat* t ms ' (a) a nuceus Il
1.12 The pholOelectric work fun~tion of . . a (jIlrbon saml) e, the following s)'s e . t of 10' eV
the momentum density of the wave. (b)
I)()t.usium is 2.0 e V. SUPI)();l.ing that light ~catlenng. I~ k:; bSl"rvcd in a direction b er'''' in the amoun ,
" this momer) tum is absorbed by the !lOr mg en OJ b' 1 eV (c) s malecule
tered radllltlOn a t of incidenre. "'ind: (b) an atom absor IIIg ,
esrth's lIur(aoo, compute the radiation having a wavelength of 3.6 X 10-7 m
falls on I)()l.as;jium, find: (a) the stol)ping
perpendicula~ to l~~f the !ICllUercd radia- ab!orbing 10- 2 eV.
ptelll!ure on the carth.
potcntial of the Ilholoelectrons, (b) the (a) the wa\h"k~g t' c energy and dircction I ')6 Sodium atoms sbsorb 0,' xCI~lot _~l~-
1.7 nadio W:WC8 re~i\'ed by a rlldio set tion, (b) t e 'Inc I _ _ . . d' tlOIl of ,5. ,
kinetic energy and the veloeity of the fll.!!t- of molion of the reooll electron". tromagnetle ra III . f the
have an electri(,l field of amplitude equal est electrons ejeeted. r to the yellow regIon 0
to 10- 1 V m - I. Assuming that the Wlwe I " Referring to Ihe I)receding ,l'rOb,"""m; oorrc;opon( Ing . e the energy
l.13 A uniform monoehromatie be.am of visible speclrum. l?etermm bsorbed or
can be consid~rcd II.!! plane, calculate: 'f. the electrons 1'(,001'1 a tnnangeo, () of the photons willch are 6
(a) the amplitudc of the magnctic ficld,
light, of wavelength 4.0 X 10- 7 m falls I . I . idcnt radiation, fim: a
on a material having a work function of relll.tlve to tIe mc . . f tIle SCIl .... ('mittl."I\. n
(b) the aV('rago intcnsity of the wave, the wavelength snd dlrecllon 0 f I 21 (a) The 10l1gCllt wsvelength thllt Cll.
(c) thc nverage energy density, (d) the 2.0 eV. The besm has an intensity of .. ra(,.111. (''0 , (b ) the kinetic energy 0
ten,.., . lallCC radiation ill mercury IS
nverage momen tum density. (c) ,\ g. 3.0 X 10-9 W m- 2. Find: (a) the num- produce ~~ What is the first excila-
the eleetron. f
ber of electrons emitted per 1112 lind per 8,
surning thllt the r adio sct is I km from the F' d thc energy and wavelength 0 p. 2.536 X I Ill. ? (b) The emig.
(b) the energy absorbed per m~ and per 8,
broadcllSting sta tion snd that the Million
(e) the kinetic energy of the Ilhotocleetrons.
:)~:ton I~at ean impart a maximum encrgy 8ion tion potelllial of mercury. shows strong
Bpcctrum of mcrcury ~ 2,536 A,
radiates energy iijotropiclIlly, dctermine f 60 kcV to a frce electron. lines at w[welcnglhs of ,18M!. , Iw
1. 14 The binding energy of an inner elee-
the pOwer of tho station. [flint: Recall
tron in lead is 9 X 10~ eV. When lead is o be of monochromatic x-rays A MOO J. and 5780 ,\. '\ here arc a
that if the cleclr'i c field vsries harmonically 1.20'\ am f 10- 11 m strikes a 3\32 .' '02 Aand 12072 A. Ca\cu-
with an smillitudc Go, the time average of irradiated -with a ccrtain electromagnetic wi th a wa\'el~ngt~\: $cattered mdiation wcak hnes at 14 of these transitions lind
the squtLre of the field is,eg.j radiation and the phot.oelectrons enler a Ihin metal fOil. I OOQ and (b) OOQ. la\.c thc ellcrgy . 'Iar to
magnetic field of 10- 2 '1', they describe a ' observed at angles of (a) .,' . set UI) an energy level spncing slm~ _36 ~
1.8 ~how that Lhc intensity of the rlldia- IS . frequencics WI ...., .. \5 (b) knowing that the . o .
tion coming from a small holc in the Willig cire1e of radius 0.25 Ill. Comlllltc: (a) the What two pre<ianllnsnt
I:,g .. 1- i~tcd with the excitation [rom
Ime IS ~slate to the first exeited slale.
momcntum and energy of the electrons, dctected in each case?
of a ('avily which ill in thermal equilibrium
"' ilh the radiation (i.e., a blackbody) is
(b) the energy of the l)hoU)ns absorhcd. 121 Show that when a free electron Iis thc groun . (ace Problem
Ll5 When a certain mctal surface is illu- . .... direction makmg all ang I' I 2S The sodium D ImC!l d I
given by I - !tt::, where.; ill the radia tion !IClluen_ " 11\ a CIon . h sodium is bombar C(
energy density. Also 6how that the Ste(an- minated with light of different wa"clengths, .p with Ihe Incid~nt ~lho~:: in :f t~~n~leo 1.26) appellr w en . accelerated by
Boltzmann consLant ill f1 _ tea, where the stopping potentials of thc I)hotoeleo- !ICllttering, the kmellc e gy by electrons ~'hcn the) ra: "olll!. ('0111-
a I)()tential dlffercnce 0 . 11
a - 7.56 X 10 - 10 J m- 3 K-4 (.see Ex- trons are measured M shown in the table. tron is
.aml,le 1.<1). Jlute the value of h, t.
A(X 1O ~7 m) 1', V A(X 10- 1 m)
Et _ b (2a cos, . )/(1 + a ) 2 - a 2 C05~ .p1, I 29 To SCll&rate t hI' car bon and oxygcn 'd
l.9 Wri te the lll:Iymplotic form of I'lanck's I', V . the carbon monoxl e
radiation law ( E(I. 1.8), for a caae in which aloms that form r \1 eV is
3.66 1.48 4.92 "'here a _ h"/m~2, . lecule a minimum energy 0
the fr<'queney i~ \'ery high Ilnd one in 0.62
4.05 LIS 5.46 0.36 Show that, in a Compton scatle rl~lg, 010 . cd' "'ind the minimum frequency
which it is vcry low. The first relation is 1.22 , . between the angles defullng and rcqUlr . I th of the clectro-
4.36 0.93 5.79 0.2' maximum Waweng. dissociate
called Wit,,', r(ldialion law and the llecond the re atron red hoton and . ,.dilltion reqUIred to
the dire~ti.ons of th,: s(~~:) ta~ iO, wherc
magnetIc
!JI called the lla!Jlei(/h_JtIJ~ radiation law.
Plot the stoPI)ing potcntial as ordinate the rewl l IS cot.p the molecule. f tO~ V
/ 1.10 What i.'! the wavelength corrCSJ)()nd_ h/iI ITl~2. \ 30 A photon having an energy 0 ~\
against the frequency of the ligbL as ab- (f _
ing to the ]leak of the blackbody radiation . hea1n. of elcctro- " '-_A bed by 1\ hydrogen atom at rest. . S
scissa. From the graph determine: (a) the I 23 A monochromatIc . f rs a..-.f . . ed in the SIlme
spectrum at 300]( (room temperature)? a result, the cleelron IS eject.. Keg-
threshold frequency, (b) the photoelectric . d' fon has an 111 tensity 0
Determine the mo n ochromatic ellergy den-
sity a~ thi~ wal'cllI l1g1h. work function of the met&l, (c) the ratio ',n~~ne~~ ra":~~t is the average numbed.' dircction as the incid,,~~a!:;~;9.t~ the
hie. m.
of photons pcr m
3 for (a) I-klb ra 10
.1 lecting thc energy r~q~)r find the momen-
I.! t Assu ming thut the sun is a spheri cal eleetron (about 13.6 c , d f
I.IG A photon having nn {'nergy of 104 :lV waves an d (b) 100i\\cV gsmmlL rIL~ s.
blackbody with l\. rsdiu.'! of 7 X t08 m, , . hI. . tensity that tUln an d (" I' encr"v of the eleetron an 0
collides with a free electron at rest and i~ eJ
calculate thc ~ uu' "'S temperature and the 1 24 The minimum 19 \D . b (
scattcred through an Ilngle of {lO0. l~ind: . be perccl\'-'U
can . ,.,' by the cye IS a ou the proton. msstrahlung
radiation cncrgy df'n sity within it. The 1 31 What is the shortest brc
(a) thc changes in energy, frequency, and ~IO W m-2. How many photons per~-
illtellsity of the su n's radiulion Il.t the sur- . b r\'ed when an electron ae-
wavelength of the photon, (b) the kinelic 10d (wavelengt, I '6 X 10-7 m) enter the wavelcngth 0 se . I d'!lerence of
face of the carlh (which i~ 1.,5 X 10r l m . .,
encrgy, momentum, and direction of the on h' . tensity? Theilupi celeratcd through a potentlll I Ihe anli-
distant from the 81111) i~ 1.4 X 103 W m - 2. reooiling electron. pupiJoftheeyeat.llSlllas05X 1O-4 m2. 40 kV is suddenly Slopped at
arcs. may be conslderl'ti .
 50 Th~!ol.ll!dalion' oj qUO/lfum phYlics Pr06lmu 51

cat~H)(le of an x-ray tube? Determine the velocity, e\'en under relativistic condi- differ by the constant amount h. Relate
reduce the intcnsity of an incident !)earn
I1'g.'OIl Of. the electromagnetic spectrum in with the e~p[anation associated ",,'i lb
whIch tillS wa\'elength lies b), f " ~~ X-~Il!S to one-half it-s original intell~iIY. tions. Also sho"' that the phase velocity
of th~ ytter field at relativistic speeds is J.1g. 1- 29.
Fig. 1- 13. re eTtlllg to . 0.... ~t %1/2 - In 2/I.. Find lhe half.
\ 81ue thH:kn~ of lead fo 0 I 0 5 1.52 Find the line width and frequency
1.32 In . the upper atm06phere molecular I:\IV r,.,8I1d equak~f/'.
1.47 Suppose that a beam of electrons spread for a I-nanosecond (l0-1I s) pulse
o.~ygen IS di'lSOeiated illto two o~ygen
r . ex-ray",
I . ("im'. Hefcr , 0 ' ""Ig. 1- 19
from a ruby laser (" - 6.3 X IO-~ m).
, or t le.coefficlents of linear absoq,tion ., "'ith a de Broglie "'avclength of 10- 5 III
.a oms bYh \lloton~
I from IItA"'"0.'em 'f"' a x - lA() -X-rays are passed 1I _rollg h aluminum paMe$ through a ~Iit tO-I m .... ide. What 1.53 If a lfOurce moves with a "elocity u,
IIn.um I' 0101l lI'a\"elength which ea~ f"] h
angular epread is introduced because of relati ve to an observer, the frequency of
01 s, ~ae of thickness 4 X 10-3 m. The
1~1 " ~lfOC{'."8 is LiS X 10 - 7 m. What is the the radiation measured by the observer
bllldmg energy of 02? roountmg . rate of a ("eig, r counter Il! a difl"r6.elion by the slit!
suffenr a shift.o" - pu/e, where u is posi-
u~('tlon JOf the number of foils is 8 X 103 1.48 ,\ probe must alway" be emaller (at
1.33 .Correct I::q8. ( 1.40) and (1.41 ) to 4.1 X 10 ~ 2.8 X 103, 1.6SX 103, {l.iX 10; least by a factor of 10) than the object tive (negative) when the motion is toward
~ake mto account the recoil effect of the counts/mm for 0' 1, 2, 3,and 4 fOIl" s respell- being studied; otherwise there will be (away from) the obsen'er, and where ~

lOll. l 'sing the corrected equatiOIlS com tn'cly. Calculate the linear l1b~ ," significant perturbation of the position would be the frequen cy if the source were
IlU/e the minimulll ellergy a PhOIo~ III ~ eocffic"c t f l ' rJl Ion and velocity of the object. Calculate the stationary. This is called the dectromal/-
. I n 0 a umlllum. From rig 1-19
hal"e to iOlli:c the hydrogen atom. useslllnatc the energy of the x-rays.' , IIdic Doppler $hift. Since the molecules in
lIlinimum particle energy if (a) photons,
1.31 Show that, in the re~-ombinatioll 1.4J .How mllll y I18 If-va Iue layers of 11 (b) electrons, (c) neutrons are used ttl probe a gas arc in random motion, the Doppler
proC('~, '\.+ + e ..... A is impossible with_ mat~rlal arc nCt'<'S5ary to reduce the in- a nucleus whose diameter is 10- 14 m. shift is differcnt for each molecule. This
out I"lohtnlg ('ith('r the COllscI"l"ution of tenSity of an x-ray 1ll)1I1l1 to (8) --'- (b)~ . 1.49 The velocity of a proton in theX-direc- introduces a line iJroadcnillg, givcn by
cll~rgy or. momentum, \lnle~s th ere is n and()~. f' . 6 _ 2{~/c)v2kTln 21m, where m is the
c 2-0()" 0 Its Incidcnt valuc? IT 1111" tion is measured to an accuracy of 10 - 7
thIrd partIcle. mass of the mo[ceule and T is the absolute
1..J2 Calculate the de Broglie wavelength m 5- 1. Determinc the limit of accuraCy
I.as
. Prove that ,in .. Fq. ( I . 42) ,eonscn'n_ with which the proton can be located temperalu", of the gas. Compute the Dop-
of nn electron whcn its energy i~ ! V
~Ion ()~ momelltulI1 and energy would be 100 eV , 1000 e V. II'h nt wnl'elengths ' , simu ltaneously (a) along the X-axis, pler broadening at room temperature
unl)Ql;:;lble if there were nOt matter (a (b) along the Y-axis. Repeat for a case (300K) for the 4.8G-eV atomic transition
":ould be significantly diffracted in a
lIucleu~ !lllellSt) l"Jrt'!lCnt. in mercu ry and for the 1.33-:'IleV nuclear
n.,ck~1 ery~lll.l, in which the atomic separa- in vjhich the particle is an electron.
1.36 .\ 2.!J...\leV "hoton, pas.sing through uon IS about 2.15 ? Calculate the energy transition in eONi. DiscuSll in each case
I.M! The I>osition of an electron is deter-
~~lId , cre.lltes an eteetron-r)()!Jitron pair of those electrons which are Brag -dif- mined with an uncertainty of 0.1 I\. Find
the effect on resonance absoq)tion.
I he Ilarucle8 have equal kinetie BO" ' . fracted at IlIl angle of 30. ,g the uncertainty in it~ momentum. If the 1.54 The gamma-ra), line emilted by 1911r
F" I ( ~ ... rgle!!.
1m: a) the momelltulIl, (b) the energy electron's energy is of the order of 1 ~ has a mean energy of 129 keV and the mea-
1.43. :'I.lonochromlllie x-rays (" ; A)
and. (c) the velocity of caeh. Xegtee~ th~ estimate the uncertainty in its energy. SUfC(1 width of the lille M half-maximum
are InCIdent on a Mmpte of KCI I
reCOIl energy of the lead atom. \ ft h - l)(lw(er. Repeat for a proton confined to a nuclear intensity is 4.6 X lO- s e V. Estimate
. ~t P otogl"llJlhie 1,late i ~ 1,la('C(t per-
1.37 ~Yhat ill the greatest 1>O.'lSible number pendIcular to the incident .,- I" diamelt'r (= IO- H m) with an energy of (a) the mean lifetime of the excited slate
~am, ael.
of ]IOSItrons that may be created by a 130- t t.he order of 2 :'IleV. emitting this line, (b) the ",Iative I"elocity
a.noo of 1.0 m from the powder. DeIC'-
:'-IeV . photon Il.S it passc~ through a ml~~ t?e first- and !!econd-order Bra r 1.51 Show that the path in Ilh~ space of
of lfOurce and observer which is requifC(1
mat.-nal?
radll~ gIven tha~ the Bragg plane !!ella !~ the I>oint representing a harmonic oscillator
to gi\'e a finrt.-ordel" Doppler shift equal to
the measured line width.
1.3$ Gamma raya with cnergiell of 0.05, tIOllls3.14A. r of angular freq uency w ie an cllipse of !!emi-
0.3,.an~ I :'-leV, but with equal intensities, 1.44 A narrow beam of thermal neutrons axes .1 and m",.I, ,,here m is the mass of I.as Show that the maximum change
are IUrldent . "" ~r. "1"1 Ie I"mear Jl~Uced ~Y a nU.c1ear reactor falls on a
on a Icnd ab," the oscillator and .-t is the amplitude of its in kinetic energy of a Jlnrtide of mallS Ill,
a bsorpllon 3 eocfllcients for ,h ,-, , energIes ' mOlion. Find the area of the cHipse and with initial kinetic energy E t , when it col-
8 cr)stal WIth h~tllce 8113cing of 160 A
are X.I O m-I, 5X 10 2 1Il- I ,and 78 m-I, lides with a particle of maSll .11 initiaUy at
Determine the Bragg angle such tJlIl~ 2 eV show that it is equal to 21fEl w, where f-.' is
~JlCet!\eIY. (a) Calculue the thickneS:! of neutrons are strongly diffracted. the total cnergy of the oscillator. Compar- rest in the JArame is .o,E~ - - 4Af.\1
cad nee<:!S$ary to reduce the intensity of ing this value with Eq. ( 1.7), verify that +
(1 11)2, where A _ Ml m. (a) Find the
e.ach beam.(o one-tenth it.~ original illten- IA5 Show that thc ralio of the de Bro,r t he area of an allowed ellip!lC is nil, Ilnd limiting vilitle when ,II m. (b) Plot
wa\"clen g th to t IIe Compton wal"elcllgth "
~Ity . . (b) Whnt is the ratio of the total hence the areas of two successive ellipses .o,J-: t tiS a function of /t.
for the same pllrticle is equal to
lI1tenSl\y (of all three rrh%n energies), at
a depth of 5rnm 10 the / t I' ' 1
illtensity? ' 0 a lIlClt ent L

1.39 Th~ Iwlj-I'a/r,e thukllt" ZI/2 is defined

.I .46 \' erl'ry t IIe fact that. the groul' \'e[oc-
IlS the tlllekncS<! an ablfOrber must ha\'e to
lIy of a wave packet is equal to the particle

2 2.2)
QUANTUM MECHANICS
2.1 i ntroduction
2.2 II'Ot'e Punction and Probability Density
2.3 Schrodifl{Jer's Equaliorl
2.4 Polen/ial Step
2.5 Particle in a PoLen/ial Box
., 2. 6 The Ilol'f/lonic Oscillator
2.7 Energy LCl'e/s and Ii'Ot'e F'unclions in General
2.8 Potential Barrier Penetration
'2.9 Symmetry, Wa L'e FUllciiolls and Po "
9 10 TI T ' ,. rty
-. Ie IInc-Dependent Schrooillfjer Equation
2.11 Transition Probabilities and Seleelion Rules
2.12 The Formal Theory oj Qllonlum Mechanics
,
53
2.1 InlrOflllrtlon
The mction of the bodies we observe around us can be described (independently
of the interactions among them) in lenns of general rules based 011 experimental
evidence. These rules or principles are : (1) the conservation of momcntwll, (2) the
COIlSt"rvatiOIl of angular momentum, alld (3) the conservation of energy. Based on
these conservation laws, a fonnalism, called cilJ8ftwl mechanic8, was developed for
describing the detailed motion of particles, under the assumptions that the parti.
cles are localized in space and that we can observe them without appreciably dis--
turbing their motion. These assumptions are, in general, made implicitly, rathe r
than stated in a precise way. This formalism has been used to desc ribe and analyze
the motions of various bodies, ranging in size from planets at olle extreme down to
electrons at the other. However, when applied to the motion of the basic constitu
ents of matter, classicalmechanies gives only approximate results; in some instances
it is entirely inadl!(luate.
WI! saw in the preceding chapter that, as a result of experimental evidl!nce, we
have becn foreed to introduce several new and revolutionary concepts into our
methods fo r describing the behavior of matter. Although the laws of conservation
of momentum, angular momcntum, and energy remain valid, the uncertainty
principle forces us to renounce any detailed desc ription of the motion of atomic
particles in the sense of classical mechanics. The quantization of energy (and per-
hap!i of other physical qUAntities) is another novel idea which does not appcar in
classical mechanics. A satisfactory theory must contain infonnatiOIl about the
allowed energy levels. The interaction of radiation and matler by mCll.ns of the
absorption or emiS$ion of photons is another new concept to be incorporated.
Therefore the situation has required that we develop a new fonnalism, called
quantum mechanic" which has produced a profound revolution ill physics. Quan.
tUIll mechanics in its present form is the result of the work of Louis de Broglie,
Envin SchrOdinger, Wemer Heisenberg, Paul Dirac, :\ Iax BOnl, and others who
developed it in the late 1920's. Quantum mechanics is essential fo r the under-
standing of the behavior of the fundamental constituents of matter. The theory
is mathcmatically elaborate, but. its basic ideas aTe relatively simple. I n this chap-
ter we shall brieRy discuss some fundamental asl>CCts of quantum mechanics,
enough so that we shall be able to apply the theory to the analysis of atomic,
molecular, and nuelcar structure, which will be considered in the following chapters.
2.2 " ' IIrt' F"nelltJft .Ift,IIrolu.'lilitU Ilt!nsitU
In Section 1.1 2 we concluded that we cannot talk about the t rajectory of an
atomic particle in Ihe sense of classical mechanics. We cannot, for example, ask
whether or not the electrons move in ell ipticnl orbits around the !ludeus in an
atOI11. This question would be meaningless even if the forces acting on the particles
produced such classical orbits. But. if we cannot talk about. the lmjcetory of an
electron or of any other atomic particle, how may we describe its motion?
T he information to answer this question is provided by the malleT field, which
was introduced ill Reetio n 1.10. To obtain such information, we are guided by our
knowledge of standing waves; i.e., waves confined to a certain region such as a
 " Quanlum muhllfliu (2.2
2.2)
!Vate functwl! (Ilia probobilify dtruify 55

vibrating string with fixed ends, 8/\ oscillating air column closed at both rnds, or . . .. h . The intensity of the matter field , given by
electromagnetic I1ldiation trapped in a cavity which has perfectly conducting walls. tion Is~sclnatUJg m suc a region. . . I that
We recall that ill standing waves the amplitude of the wave is fixed at eaeh point
It(!l:W. is indicated in fig. 2- 1(b). To be more quantitative. et us say
of space. At points where the amplitude is larger, the wave is more intensc. Ihe probability 01 jil,dillg the parfiJ:ie des;;riOOJ. by the It'aVe function t (x)
2
A similar situation occurs in the case of atomic particles. Consider, for example, in Ihe inlen'al d.I: Ground the l)oil1/ x il 1,,(x)1 dx.
an electron in an atom. It never moves too far away from the nucleus; it is CSSCIl-
tially CQnfincd to a small region of space with dimensions of the order of 10- 8 m. In other words, the probability per unit length (or probability denaify) of finding
Thus its llSSOCiat.cd matler field may be expressed in tcnns of standing waves local- the particle at x is
ized in this region, with the amplitude varying from point to I>oint within the region
and being practically zero outside this region. Let us designate the amplitude of P(x) = 1,,(x)12
the matter field by 4-{:I:) . This amplitude '/I(x) is currently called the u'tU'e IUlldion
for historical roosons, although the name is misleading. Perha ps it. would be better We are assuming',for St~ml)l.i,',;,t~,l,ha:h~I~.~~~t;~::ci:i~:~
,;r
e
~~r:e~~:I~n;~p~t:~~)
just to call it the maJterjield amplitude. the general case 0 mo Ion I ,,- , I( )12 d d dz
We know that th~ intensity of a wave Illotion is proportional to the square of the depends on the three coordinntes x, Y'.z !tl~at i~, ,,(X'I y, l~ldxT~:I~: ::O~r;d th: ~illt
is the probabilit,y of finding the particle til tIe vo um
amplitude. Therefore the in[enaity 01 the mal.ler field is given by 1'/I(xW. The wave
having coordinates x, y, z, or
function '/I(x) is sometimes expressed by a complex funct ion; that is, a function
containing i = v=r. The complex conjugate of a corllplex function is obtained p = I,,(x, y, zW
(2.1)
by replacing each i by -i. The complex conjugate of a function '/I is dC8ignaled by
,,*. Then 1"(x)I~ . '/I(x)'/I(x). For a real function", = ", . Next we shnll eon. , lh, p""bability per unit volume, or the probability dellsity, of finding, the pa.rticle
" . For example suppose that we COrllpU l C .,,(
"X, Y, ,) for an e ectron drn an
sidcr what physical meaning is ascribed to the intensity of the matter field . Since
the matter field describes the motion of a particle, we may say that the regiol/s 01 at x, y, z'd
atom,an po"...,'t
1,'1' ',n' r'" ?-2
._, where N is the nucleus and the degree of ar ~
k

apace in which Ihe particle is more likely w be found aTe those in lI:hich 1-(x)1 2 is larue.
For example, the wave function -(x) for a particle confined mainly to the region
betwccn A and B is shown in Fig. 2- 1(11.). Note that ,y(x) decreases very rapidly
outside the region AB where the particle is likely to be found while the wave fune.

,.) JJ

,b)

Fig. 2-1 . (a) Wave function of a particle moving between A and B. (b) Probability
distribution corresponding to the wave function shown in (a).
 57
56 Quan/um mtchanic. (2.3 2.3)

ness is proportional to the value of I ~(x, y, zW. Thus the darker zones represent in an inttlitive manner, by analogy ~\ith otl~er .fields more familiar to the studen~
.
A , i!O, III 0 , -J P
Ot-"C Ion _. -,
we slmll indicate , II"lthl1l the fonllal context of qunntu
the regions ill which the probability of finding the electron is grealest. This state-
ment is the most. we can say about the localization of the electron in the atom, and mechanics; how the Ctlu.'\lion is obtained. . . .
it is impossible to talk about the precise orbit of the electron. In the case of a free l)artie1e thc I>olential energy 1"- zero (that IS, E,,(x) Oil 0),
The probability of finding the electron within a finite VOlWl1C V is obviously and Schrodinger's C(lunlion becomes

PI' = Iv I"'(x, !I, zW dx dy dz.

Kow the elcctron must always be somewhere in space, and therefore if we extend which may be written in the form
the above integral to all space the probability becomes certainty or 1. TheIl we
must have , 'I' (2.-1)
d"' +~ >f = O.
dx2 2 h
(2.2)
fiut fur a free particle, B = p2/ '2m. Setting fl = hk, according to Eq. (1 .-1. , where
This ex])rcssion is called the lZol'!1!alizalion condition. It imposes a severe limilation k is the wave nUl1lber, we have I~' = l! ~k2/2m. T heil Eq. (2.4) \)ccomes
on the possible forms of the wave function 1/-(x, y, z), since it is not always possible
to satilSfy Eq. (2.2) for an arbitrary function. I n particular, f(x, g, z) must elcclcase {p", + e", = 0, (2.5)
very rapidly when the coordinates x, y, z arc very large, in order for the integral dx'
over all space to e:dst. which is identical to the ('{Iuation for the amplitude of ~:a~lding w~\"es. with a wa~;
,engl,, ~ - ?7I'/1.-
_ = hlp , as rl'<luired by E<I. ( 1.4-1). 1 1m
.equation
. IS obeyCtJ,
lumnor
,"
example, by the amplihl<ie of ~tandiJlg. wn:es on a s1rlllg or III a gas co
2 , :1 Sf'hrfjfllngf'r'lf Equation
electromagnetic waves trapped III a CiWlty. . . . I 1.
Our next step must be to find a rule by which the field amplitude or wave function HClllembering that i = " q and ;2 = - I.' we scc, by direct ~ubstJt utlon , t la
f can be obtained for each dynamical problem. Obviously the wave function f(x) the difTerential ('{Iualion (:Li) admits as solutions the wave functions
must depend on the dynamical state of the particle. This dynamical state is deter~ ., (2.0)
milled by the forees acting on the particle and by the particle's total energy. But ", (x) = eiJ:~ (IUd "'(x) - e- .
if the forces are oonscn-ati\'e, the motion is detennined by the I>otentiai energy As we ~hall see in Section 2.10, the wave function f "'" e represents a. ffCC. part, ,.
ih
E,(x) of the particle_ Thus we may expect that the wave function f(x) must , ~ I.' 2/2 h2 k 2/-J1II movUlg 11\ tie
ole of mOlnentulll P = hk and cnergy t!. = p m .,. - - r 1
depend in some way on the potential energy and the total energy, .
+X. <lireclioll, and the wavc runction" = t ,t, _..t.< represents a free particle 0 tIe
. ....
t: = pl/ 2"" + t:,,(x) , same momentulll and encrgy but mo\ing in the OI>I)()!;lte?r _.\ ..{h~tlo.n.
The general solution of E(I. (2 ....,) can be written as a. linear comblllatioll of the
of lhe particle. In fact, the rule for finding f(x) is expressed in the form of a dif~ two solutions given in Eq. (:tG); that is,
ferential C<1\L8tion, eallcd Schr6di"yer'! equation, which was fonnulatc<i in 1920 by (2. i )
the German physicist Erwin SchrOdinger (1887-1961). This C<luntion (for one-
dimensional problems) is
This wave funci ion docs not corre;I>ond ~o ~ prcfcrrc<~ direction .of .mot~on. b~\l::
2
h d f, 2
, the superposition of the solutions f()rmotlOn III the +.\ .. anu - .\-{hrecIIOIlS. d.
- 2m dJ:2 + E,,{x)f = E"" (2.3) is the ~ame si tuntion foulld in sllLlllling waves,. ~n('al1, for exnnlple, th~t st~n b!;~~
wnves on a string result from the sUpCTJ)O~ltlon of wa\cs propagatlllg III
where til is the ma.~s of the particle. Schrooinger's C<luntion is as fundamentril to directions and rdlectc<i at the fixed end!:!.)
quantum mechanics as Newton's equation F = dp /elt is to classical mechanics or :\otc that Eq. (2.(;) yields
11 laxwell's equations arc to electromagnetism. Obviously the solutions'" of Eq. (2.3) ih
depend on the foml of the I>otentiai energy Ep(x). If(.I")\2 = ",(x)", ex) = e- ih . e "" L

We shall not make a detailed derivation of Sehrodinger's equation, since that.

would be Jx.yond the scope of this book. Instead we shall justify it in Example 2.1 Sce !-'IJlldumtlllal ["lIit"fnily Plty~k ., Volumc II, Scction~ 22.4 through 22.9.
 $
,. Quem/urn mhllflicf
(2.3 Poltnli/ll tltp 59

The fact that [!f(X) [2 = I, or a constant, meall!! that the probability of finding the
~ I .
particle is the same at any I>oint, In olher words,.f = e:l::..t.. dCSl.:ribes a situation Although when we ..... rite the 81anding-wll\'C equation we assume that k ,IS eonll~ant and
that lherefore.p should be constant, this is not generally true fo~ a II&.rlltie subject to a
in which we have completc uncertainty about ]>osition, Thi$ is in agreement with
f lI owever we ghat! use the above equation even whell P 1~ not constant. Then,
the uncertainty principle, bccuuse!f = e:l:: ih dcscribCII a particle whosc momentum, orre.
fCmembering , the total cnngy 19 E _ /I ~I 2m
that +.' ( ) ,
r:.. x , we nllly IHI'te
1) = hk, we know ])rccisc!y; that is, IIp = 0, which TC(luir<:-s tlmt.1x _ 1Xl, To ob-
tain information about the position of il particle localized within a region !lx, we
must. therefore supcrposc sev('I'Il.1 solutions of the form A eik~, wilh different values
of k (or p), snd with appreciable amplitude A in a range!lk (or !lp); that is, we and thus the abol'c equation becomes
Illust form a wave IJacket (see Fig, 1- 2(3). This w:\ve p:lcket. C1U1 be expressed in the
form i" + 2m[t.' _ EPII"'
(. )'" _ 0,
.J.(x) = f " (k)e ib
dk, (2,8)
dz:2 42'

..... hich if we make 11. slight rearrangement or terllUl, is JUSt Rchrudin/tcr's ~uation (2.3).
where A (..1:) is the amplitUde corrcsl>Olldiug to the momentum p = hk, We nl~sl emphasiU', ho .....e ..er, that we hase lIot dcn,"ed Schri'M:li,nger' equatIon, but have
Schr6dinger's C<luation (2,3) describes a particle moving in a straight line (one- simply, by means of analogy, traced it.'! origin back to the rdatlon.'! ( 1.44) or (1.45).
dimensional motion). For n particle moving in SI)8Ce, the cquat iOll bccomCil

-
(a'>{I a .f a~.f)
h'
2

2m ax2 + ay2 + al' + Ep(x, y, z).f =

,
1/-, (2.') As B. first illustration of the usc of SchrOdjngc r'~ ~ua.liO~lJ let us dcte~mille the
wave function .f(x) for a particlc moving in a regIOn m willcl~ the pote,tI,tllll ~nergy
which is the obvious gellcruliziltioll of Eq, (2.3), with the three coordinates appear-
ing in a symmelric way. In the ease of a frC() particle, Ep (:.t, y, z) _ 0, and the
,!e
is as illustrated in Fig, 2-3; this situation is called a p<Ilelllial p. I hat IS, tI.le
cquation become; potential energy is zero for x < 0 and hM the constant valll~ ~o for :r: > 0, !\o
physical potential exhibits such an abrupt or sudden change; It IS more ~na~le
2 2 to expect the change ill potential to be smooth, ,as shown by the dashed ll1~e. I'or
.' (a
y, Y, a
ij2.J.)
- 2m a.r2 + ay2 + az2 = Ey", example, free electrons in a metal experience lIus smoo~h chang~ of potcntlal. near
the metal surface, However, the nonphysical potential. 8t~ l) 1.8 math~llall~lly
The solution of this C(IIUltiol1, which de;cribes a free particle moving with momen- simpler Il.lld its rcsult3 are Il.PI>lieable to actual eases, as all IndlcallO,n of ~he phYSical
tum I' = Il k and energy E = 1I.2}.:2/2111, is situation, It is nece:ssary to consider separately the cases fo r which E < E() and
for which E > Eo.

We lcave the verificilt ion of this to the slmlent, who lllUSt recall that

and
(I) J,:,- Eo
f;XAMPLI,; 2.1. Imultil'e ju~ tificati on 01 Schrooinger's equation,
Sol .. ,io/!: We have !;3id that, in qUllntum mechanics, the wave fun ction .f(z ) Jl]sys a
role similar to lhe arn plitudc ~(;r) in a standing wave, For one-diml'rI~ional wal'e motion
Fig, 2-3. Potential ~tep. (In, this and
(
..
the amJllltude of 9 standing 1I'III'e of \\'al'clength)' SIltisfies the differential equalion,
,
<!J + k2~ _ 0
aU succeeding figures the elassu:ally for
bidden regiolls are shaded,)
(II )

! x
dz;2 ~ ,
"
where k - 2,,!X is ~alled the U:(I('(, ,uwll!cr of the standing \\'ill'e, Noll' we recall from (11.) f: < Eo. in th is casl', clllS!Jicnl ,mce,hanies tcll~ us lI~at tl~; particle canno~
Eq. ( 1.<15) that in quantum mechanics p _ Ilk, so that we may expect the W9\'e fuuetion be to the right of 0, becausc then the klllctlC energy J~ k = ,f. - Co ~ou~d be ncg,a
.f(z) to Mlisfy a similar equalion of the (arm live which is impossible. Thus:r: > 0 is a classically forbidden regIOn If E < ~o .
J!y" p2 Thi~ means that in the ca.sc of free electrons in a metal, those electrons With
dz;2 + h2.f - o. E < Eo cannot:scapc from the metal ; when they reach the surface of the metal,
they are turned back into it.
 60 QII(III/lIIll mtchonic, (2/i 2.4) Poknlial r/tp 61

To obtain oJ-(ol) for a potential step we mus t write Sehrodinger's equation 8CI)8.-

crosses the potential step. This requires that
nndy for the regions z < 0 (or I) and x > 0 (or II). In region (I), in which
E p = 0, Eq. (2.3) beeomes and doJ-l doJ-2 ro r z _ O.
dx = liz
d2't!
dol2
+ 2mE .1.
h 2 ,..1
= 0
, These conditions yield A +B = C and ik( A - B) = - aC, which in turn give

which is id('nlieal to &1. (2.4) for a free particle. Its generol solution is of the tYI>C
B _ (ik + a)A and C= 2ikA ,
\ - ik 0 ik - o
givell in &1. (2.7), or
so that

In the way il is writtcn it represents an incident particle (eih)

(2, 10)

and a reflected
, -.
2ik A - '
oJ-,(x) = - ' , - - , '

particlc (e-'*'"). We arc assign ing a different amplitUde to the rdleeted particle to
In the rorm we have written oJ-l! the intensity of lhe incoming field is IAI2. The
take into account any possible changc of the incident beam as 0. resul t of the intcnsity of the reflected field is
reflection at ol .", O. In region (I I), in which E,,(ol) = Eo, SchrOdinger's (''<Iuation is
2
d oJ-2
d..r;~
+ 2111(B1!-~ 8 0) .1.
"' 2'
= 0

(
2. 11 ) Therefore both the incidcnt and the renected fields have the same intensi~y .
We may interpret this result. by saying that all particles reaching th.e pote~tlal
When E < Eo, w(' may definc the positive qua ntity a 2 = 2m(Eo _ E )/h 2 , so step with E < Eo bounce back, including those. that. penet~te ~hghtly moo
thaL thc difTerential equation (2.1 1) beeomes region (II). This inte.rpret.&tion is in agreement WIth the phYSIcal pIcture of the
P"""""
The functio n oJ-l (X) can also be written in the altemate fonn

T he solution or this differential C<luation is a combination of the functions e<U

amI e-"", as we may verify by direct substitution. But the incrcnsing function
, -.
oJ-I {Z) = - :A- , [(iA:: _ a)e;h + (ik + a)e-ihj
e"Z is not acceptable because we know that the field amplitude is very small in and, remembering that e<h = cos kx j sin h, we obtain after multiplication,
region (II); eS I>erience tells us that we are not likely to find a particle in that region
(recall our statement that, classically speaking, it is impossible). T herefore we
must usc only the decreasing exponential funct ion e-<U, or
.f1 (X)
2
= ik : aA (COSh - ~sin kz)'
Thus, disregarding the common complex factor 2ik/ (ik - ~~ which multiplies
oJ-l and oJ-2, we can represent both functions by t he curves of FIg. 2-4. fTh e.la~::x
The fact that. oJ-2(X) is not zero mcans that therc is some probability of finding l he the potential energy E o> the larger the value of a ~n ~ the !aster the unctIon "2
l>article ill region (II ). This constitutes onc of the most intcl"e3ting I)ccularilica goes to zero for x > 0 for a given energy E. I n thc lmut as Eo becomcs very large,
that distinguish (Iuantuill from classical mechanics. That is, in qunntum mechan- A ,.(z)
ics, the region in which a particle may move docs not, in geneml, have shal"!)
boundaries. However, since oJ- (x) is givell by a negative (or cit..'Orcasing) esponential,
the probability of finding the I)arlicle with E' < '0 to the right of the potcntial
"
~------7'L-----=:'~------;"L---o1o1-''''''"''' --1 X "
step (that is, whe re x > 0), dec reases very ropidly as x increases. In general, the re-
fore, the particle cannot go very far into the classically forbidden region.
We can dClennine the constants A , S, and C only by applying the condi tion of
continuity or the matter field or wave fun ction at z = 0, which is an obvious Fig. 2-4. Wave function for a potential step of height Eo, when the particle's energy
physical requirement. That is, the wave fUllction must change smoothly as it E is smaller than Eo.
 Qoonlum r71haniu (2.4 2.5) I P(II"licit ill a poltnlial ba:t 63

so tha~ 01 is also very large, the function "2 is essentially identical to zero (" _ 0) Applying the boundary conditions at x = 0 to the functions given by Eqs. (2.10)
and no particle can penetrate into the classically forbidden region at th: right. and (2.12), we then have

expression for "I

(x > O~. In other words, all particles arc reflected at x = O. In this Ca8C, t he above
heromes A + B = C, k(A - B ) = k'C,

"I = 2iA sin u '"'" C sin kx, whose solutions arc B = (k - k')A/{k + k') and C := 2kA/{k + k'), so that
as indicated in rig. 2-5. (The student should compare this situation with that Of
waves on a string with a fixed end.)
78
,, ./ T he fact that B is not zero is an indication that some particles are reflected at
x = 0, which again is a result different from that predicted by classical mechanics.
This reflection is a characteristic behavior of alilieids whenever, in their propaga-
tion, they encounter a region of discontinuity in the physical properties of the
E medium. T his behavior is well known for the case of elastic and electromagnetic
wavell.

1':,-0 EXAMPI. 2.2. Determine the reflection and lhe trnllsmission coefficients of the
i 0 ~ potential step for B > Eo.
50",,;0'" Let us call D _ p/m _ Ilk/Ill the velocity of the IlRrtide in region (I) and
",) v' _ flk' lm the vdocit.y in region (II). Recall that thc intensity of the incoming pnrtides
~i g .2- 5. (a) Potential wall. The par- (that is, the number of partides pcr unit volume in the incident heam) is given by 1:112.
ticle cannot penetrate the region .t: > O.
/'t:-"'" (\ ,
Then the "flu,," of the incoming beam or particle current density (th!!.t is, the number of
(b) Wave function for a potential "'11.11.
/ V """ particles passing through!!. unit area per unit timf') is ,,1.11 2 The ~ flux " of the reflected
field is v!812, since the speed remain!! the same for the reflected field, and that of the
transmitted field is etICj2. TllUS the reflection and tran!!mis..ion coefficients aTe
(I) (II )

(b) E> Eo. I n this ease, if we ngain assume that the particles come from the
left, the classical dcsc~iption would be that. all particles proc<!Cd into region (II ),
although they move with a smaller velocity than in region (I). At x = 0 the parti- (.\:+ k')2
~les suffer a sudden deceleration, since thei r kinetic energy is !fulaller in (II ) than
Doth Rand Tare smaner than I, since the incoming beam of l)llrtidCll iSliplit into reflected
~n ( ~). The quantum-mechanical pic~ure is di~ercnt. T he solution for region (I)
IS still gwen b~ Eq. (2.1O), "I = Aei-tz +Be-i-t>:, if we assume that it is possi ble
+
and transmitted beams. The student should verify that R T - I, which is required for
conservation of the number of particles, since the incoming flux of Ilarticles must be
that some pa.rbclcs arc rcfleded (an assumption which we shall verify later). H ow_ equal to the sum of those reflected and those transmitted.
ever, fo~ rcgl~n. (JI ) the .solution is different, beea.use now E > Eo and we must
define the positive quantity k'2 = 2m(E - Eo)/h 2 so that E q. (2. 1 I) becomes
2.5 '."rliele in II 'ol"nllol "o.~
2
d "2
dx 2
+ k,2,,2 = 0
.
Consider, as a second example, the case of a particle constrained to move in the
region from x; = 0 to x; = a, such as II. gas molecule in a box. T he molecule moves
:rhe ~lutio ll. is n o\~' also similar to the solution of EQ. (2.7). One thing is certai n frecly until it hits the wall, which forces the molecule to bouncc back. A similar
m thiS case:. III regIOn (II ) we have l>articlcs traveling only to the right, and thus situation exists for a free electron in a piece of metal, if we neglect the electron's
we must wrIte interactions with the positive ions and if the height of the I>otentiai barrier is much
larger than the electron's kinetic energy. T he electron cnn move freely through
(2.12) lhe metal but eannol. escape from it.
~----------------~~--~---------------
QUIlnlum ma.hania (2~
I Ptlrlid~ ill tl poklllitlllm: 65
2.5)
,
We may represent each of these physical situatio ns by the rectangular potential 1 __- -
of Fig. 2- 6, which, like the dingrnm of the potential energy ill Fig. 2-3, is an over-
simplificatio n of the potelltial energies that actually occur in nature. This sim-
plified ])()tcn tiai energy diagram is called a lw/el!lial box. We have Bp{z) = 0 for
o < z < a, since the particle moves freely in thaI. region. But the potential
energy incrc88CS Shllq)ly to infinity at x = 0 and x = a. T hi!) means that very
strong forces act on the particle at those two points, forcing the particle to reverse "- 3
r
its motion. Theil, no matter whllt the value of the energy H, the particle cannot be E
to the left of x = 0 or to the right of .:t = a. (Remember Fig. 2- 5 and the dis-
cussion in Seetion 2.4 concerning very large Eo.) T herefore, in those two regions

(x < 0 and x > a) , the wave function is idcntically zero; that ill, ",(x) . O. I n
the region 0 < x < a, the problem ill CSlJClltially that of a free pllrticle. SchrOdin-
.-0 y--sinJ::r ,_0 .. _ 2

ger's equation for the wave runction of a free particle is Eq. (2.~). T hat. is .-, ------------------
0 , X

Fig. 2-6. Olle_dimen~iona\ potrntinl Fig. 2-7. Energy h.'vels for I!. one-
box of width dimcnsionnll'otelllil11 box.
Since the !>ilrlicle is moving back and forth bctwC(ln z = 0 and :t = a, t.be wave (I.

function (as in Ihe case of the potentinl slep) is given by Eq. (2.7). T hat is,
'f F: - 112 2( ?ma 2 is the C'nellty fo r 11= 1, thc n E = 8 1, 4E'" 9/~lJ ...
"'(x) = A e,h + IJe-iJr~, or, I ' I - 11" -
We conclude then that the I>arlicle C:U1not "we any _ar I '.
, b'tmr)' ene""~' but only
" ~,
.
I h osc \':1 Iues given;;
b' E" (.,
. _. ..I' ) "" I , hOIHI in Fig. .
2- 1; thaI ' I", Ihe energy of thc h
which conl1!.ins motion in both directions. The boundary conditions require that . IeI~ quan "120. ed T hi"~ is "\ lIew Qi tu:l.tioll , since m the prc\'IOUS cx:\mple of t e
partlc . .' I
4t{z) cz Oat.z= Oand x=a. Then "'(x = 0) = A + IJ = OorB = - II. So . I t 'c did not hrwe w iml)()SC :111\' limitations on t lC cnergy.
l)Oten1la 5 ep \\ , k _' 11 cd' ~ a I>cculi:uity
This situation of only ccrtain cllergy values ""lOg a ow IS. n~. , _
II-(z) = A (e':!" - e- iJrZ ) _ Ziti sin kx = C sin kx, ,. I ,)robtem but i~ gencrally holds whcnever Schrodlllgcr 5 ~ua
r I
o t \l~ par leu a r , I tl " I to move III a
r (" 3) . IvOO fo r a potential energy which con mes Ie par IC e . .
whcreC = ZiA. The boundary condition atz = a givcsII-(z = a) = C sin ka = O. rlOI~ -I I~ 80 (R ecall that in the case of t he potential step the parttcle IS not
SinceC cannot be zero because we would thcli have no wave function, we conclude Iml,~'" ,""gloll,. 't~1
eon \11('( un Iml '" , ~
0.,'0",w'u th\1II the encrgy is not quantized.) Energy (Iuan-
1 ,1
that sin ka = 0 or ka = 1l1r , where )1 is an integer. Solving fo r k, we have . . . d t the fnc~ that. the wnve function is dcte rm Ul('(1 by tIe potelltJ
.

l1zatJon IS '," '~lIndRr)' conditions. An acceptable wllve function II-(x), satisfyil:g

k = mr/a p = Itk = "1fh/a, (2. 13) energy all( , l IC FV I' I f tam
the boundary conditions of the physical problem, In geller11 C!.:tSU on y. or cer 1
l E E E .. . E ... of the energy. Therefore the nlnthema~lcal forma.-
which gives the possible values of the momentum p = Ilk of lhe particle. va U('8 ' I, .. ~, 3, '.' rcAACd b' Schrodingcr'>\ Q(luatioll, Hlcorporn.tcs
The ellergy of the particlc corresponding to the k-values given by &t. (2.13) is ism of (IUantlUll mcdllllllCs, as cxp .) . ' 'ed I
the quantization of cncrgy and the existence of a d.lsc~te set. of allo\\ . el e~
t .., I wa)' In thi~ I>roblelll we a.re con~\{lerlllg, we ftnd that, III ad(h-
I
Ie\'esmans u... < . ' I I t of the
(2.1 -1) lion to the fact that the cncrgy of the particle i~ quan1l7~Q( , tIe mO?~el.l urn r
particle is quantized also, with pO$~iblc values given by "'q. (2. 13). I hIS, howcvc ,
Thc studcnt may now recognize thc c):trllordinary simihrity betwccn the mBlhcma.tical is not. the gcncral case. . )
methods used in scI'cral different ph)'sical problem~, such as the vibrating string with The wave functions corresponding to the k values glvell by Eq . (2.I:i arc
fixed cnds Ilnd the present problem of a I)(lrticle in a potential box. The phy~ical8ituation
changes, but the mathematical technique remllinll the S3.me. (This is why it is so importaut (2.1 ;)
'-/I. (x) = C "in (wlu/ a).
1.0 master IKIrne basic mathematiC3 before undcrtaking the study of I,hysics.) We mus~
warn the studcllt, howe"er, agllinst thinkini: that, because the mathematical formalism
I . " idcntical with thc '1110\\'00 amplitude functiuns for .!<landing waves
ill the !!:lme, the physical siw:uions arc similar. He must not think, for e.xsmplc, Ulat Wh IC I, HI ae, nrc
.muvlr:tlllgs,
b "
" . r t' I ttl'""" el1c"'"'
to'"" with fi:ro:ed ends . T he wavc fUIlCl10ns or Ie 1~ 10 ..."
matter waves lire similar 1.0 "'!l\'Cl! along a string. ""'"
 Particle ill a potential box 67
66 Quantum mh(lJliu (2.5
2.5)

rCCiuircs thal..1x Ap ;?: h. Therefore a(2p) ;?: "or p ;?: d l a, giving E 2: E I . The
Line or "ymmctry
existence of a zero-poillt tllergy, as E I is sometimes cal1C<1, is typical of all problems
in which a particle is confined to move in a limited region.
To complete our discussion, we shall determine the OOllstant C which appears in
Eq. (2.15). The 1I0nnaliUltion condition (2.21) in this case is
L-----\-++-.L------"--J--------'-----'''---1P'---'
., C2
.
1.,
2
.
n:ll"x
6111 - - dx =

because the range of the function is from 0 to a. The value of the intcgral is !a.
Thus C~(!a) = lor C = .;2Ta. Thercfore thc Ilormnlited wa\'e functions are

f ~(x) = ,!Va sin (nula).

Anothcr interesting prOI)erty of wave functions is that thcy are orthogollal; that
is,
(2.1 6)

We may verify this in the prcscnt. case as follows : Noting that the functions f~(x)
_____ .!.'=.L______ _ arc real and thus f:(x) _ f~(x), we may write
-"-- - + - - " ' -
1.. 1.'
01' 2 . n'll"z . n'1fz
~~f .. dx = - Sln--"n--d"
o ao CI CI
(0) II,)

Fig. ~--8. (8) Firlll three wlll'e functions for n lJ3rticlc in 9. potentia] box (b) Corre-
~[X)lldlllg probability d(!flsitie~. ..
where we have used the trigonometric identities for COlJ (a (J).
levels arc, rel~rcselltcd in Fig. :!-8(a). I n Fig. 2-8(b) the probability density 1 ';~ I: It can be shown that the property of orthogonality is a geneml property of the
has bC!Cn unhealed for the same CIICrgy levels. solutions of Schr6dinger's cqUlltion and not a peculiarity of the potential-box func-
. Incidentally. in t~is simple case we could have derived the CIlCrgy values given
III Eq. (2. 1 ~) by usmg the analogy with the vibrating string. The s~udcllt. may
tions (see Section 2.12).
rocall that In onlcr to have standing waves in a string with fIXed ends a distance a EXAMPLE 2.J. Oblain the energy le\'el~ and \\'a,'c runction~ for a particle inside !1
apart, the wavelength" must have the values potential box of sides a, b, and c (Fig. 2-9).
( z
1" = a !a, !o, ... , - a
J

"
Theil 7J = II/X = Ilh j 2a = mrlL/a arc the possible values of the momentum in ,
agreement with E{I. (2.1~); lhc~'dor<l the energy is given by Eq. (2. 14). lIowc~er,
f~r more comp.l~ !>Olcntml~, thus analogy docs not. apply, and a sol ution of Sch ro-
,:',
dillger's equation IS required.
. I~ is interesting to note that lhe minimum energy of a particle in a potential box ,a, ;"---r-b

IS 1 = h27r~/2maz a~J{1 nOL . 1.C~o, as one would suspcct. Thi ~ minimum cncrgy is "
F ig. 2-9. Three-dimensional potential bo.~.
~elatc<~ to t.he uncerttl1nty pri nCiple. T he uncertainty in the position of the particle
IS, obVIOusly, ax "'" a. T he particle is moving back and forth with a momentum p'
the uncertainty in the momentum is then t..p "'" 2p. The uncertaint.y princiJlI~
 68 (2.5 Parlick in a polen/ial 1m 69
2.5)
Sollllio n , Extcndilljt our previous reasoning, we notc that the three components p.. p,. TAUU-: 2-1 Enugy Levell! and J>.cg,me rll eiu in H
and p, of the momentum of the psrticlc mus~ satisfy relations similar to Eq. (2.13) for a C ubi ca l 11o;r (E l _ ... 2A'/2ma')
onc..dimcn~ional bo:\"o Thus

rhrll
P. - - - .
P.--.-'r/l1l~
Energy

3E,
SE I
Combinations of
(I, I, \)
"I, "', l1a

(2, I , 1)( 1,2,1)(1,1,2)

Degeneracy, f1

I
3
where Ill, 112, Imd"3 are in legeI'!!. Tlms
9EI (2,2,1)(2, 1,2)(1,2,2) 3
../' IIEI (3, I, 1)(1, 3,1)(1, 1,3) 3
12EI (2, 2, 2) I
14KI (1,2,3)(3,2,1)(2,3,1) 6
(I , 3, 2)(2, I , 3H3, I, 2)
(2.17)

This c.~pre.'!8ion give! the energy lC\'cls of a pllrtic1e in a llircc-dim(,llsiollallmtentin! box, So lutiQ'" For simplicity we shall consider a cubical J"tOtential. box of side a .. The n, as
By comparing Eq. (2.]7) with I~q. (2.15), we find that the WfI\'C function can bec)(pressed we saw in the previous problem, the energy levels or a particle III the box are gIVen by
by
1/t _
.
CBin~&in IlZlI"y
, sin "3"':.
,
The sludC'Jlt should vcrify, by direct substitution of Eq. (2.18) in SchrOdingcr'8 equa-
(2.18)
1r?h2 2
E _ - - (nL
2ma'
+ n,+
2 2
113),

tion (2.9), with I~. - 0, thllt the value giHn by Eq. (2.17) for the energy also l'esult:<,
and that'" - 0 at the six ra~ of the potential box; tilis was the same requirement
impo8ed for a one-dimensional ]tOtentinl box. Note also tht Eq. (2.18) is formally
idcntical to the equation for thc amplitude function for standing wa\cs trapped in a
rectangular cavity.
where nl 112 n3 are integer6. We note that for a S!1llill box (i.e., 6111all value of a) the
ener le~cl; are spaced widely, a~ ~hown in Jo'ig. 2-IO(a). I~ut for a very larg~ box, as
is th~ca.se for m<lieeules of a gas in II container. or for electrons III a metal, ~UC~IV~ levels
are so close that they practically form a contmuOII~ B]lCelrum, as shown III Fig. 2 lO(b).
1~81

An irnpOtt.ant8ituationllrist"~ when the potential box is euhienl; that is, when a _ b _ c.

Then the Il()!!!;ible energies are ghen by

T
dE

where ,,2 - n~ + ni + ni, lind the corresponding wa\e function~ nrc

. .
y, _ C Bin It''ll: sin lrn2!1 lin lrn3<t .

Note that the energy depends only on ,,2 _

,
nf +
n~ + n~. This mellns that all atates
corresponding to all intcgers Ill, 112, and 113 which give the same value for K hlwe the Fig . 2-10. Energy levels for (~) a small
same energy. Ilowe\'cr, whcn the numbers Ill, 112, ::llId 113 are changed without changing pot.ential box, (b) II large potentIal box.
the value of ", the w/we function also changes. Thus a certain energy level mlly be aaso-
eiat.ed wilh several wavc fUnctions or dynamical states. When this happells, rklJcnera~y "':,' _ 0
is said to exist. The orde r of d!'gcnerney of an energy level, designated by IJ, isequII] to the Sm.,lI Uo~ (.. .. b_e)
number of different (or independen t) wave fUnctions for the given energy. These are I.)
iIlustmted for the first six energy levels of a cubical potential box in Table 2-1, where I~I
is equal to lt2f,'/ 2ma2.
Our problem is to find how many enerlQ' levels there a~e i.ll a small euergy r~nge d15 w~en
the pot.enlial box is very large. This problem is very 8]Znll~r to that of findlll~ th~ m : '
EXA MI'L 2..1. J)i~euss the number of energy levels in a small energy range dE" for of oscillations of wa\'cs trapped in a cavity whose dimenSIOns are mucll larger t Illl t e
a particle in n very llirge potential bo.~.
wavelength.
70 QU(IIllum mAalliCl (2.5 2.6) The harmonic Neil/alar 71

Let us introduce the coordinates t '1, t in II certain repre!!Cnlative 611800 (Fig. 2- 11 ); In some instances it is more con\'enient to use the number of stales within the momen-
each IlOint, of coordinates ~ - Dl, '1 - n2, and r - 113, represents an energy level, and p
tum interval dp between and p+ dp. Recalling tha~ the partiele within the box acts
to esch p()in~ there corresponds II cell or unit volume in this representative space. Let us 118 a free partiele, we ha\'e B .. p'/2m. Defining g{p) 80 that dN .. g(p) dp .. rI(E') dE,
defin e K2 - e+ +1f2 (2, and say that the number of points having l)(JlJith'c integral ""e have
coordinates and lying on the su rface of a sphere of radius ~ give the different stales tI.!$O-
dated with the t'nergy dN dE 4rV 2
-d, -g{p) - g(B)-d
, - - " ,.
0- -
L' "- ' 2
'11""
2ma' This expression aplIlies 118well for the number of modes of longitudinal waves Ira\)I>ed i.n
a CB.vity of volume V. t n such eases it is more convenient to use the frequency . \\ e
To find the number of 8tatc~ .'I'(E) with energy be~.... cen z.era and E, we must lind the recall that" _ 1Ij). and ... cj)., where c ~ the phase velocity of the wa\'cs. T herefore,
volume of an octant of a sphere of radius II, .!Iinte only positive \'alues of III, "2, ~nd '13 defini ng g(.) so that rI (.) d" .. g(p) dp, we have
are allowed. T hUll, remembering that h _ h/2r, we obtain
dp 4rV 2 (2.20)
g(~) .. g(p) d" .. ~" ,

which is a very useful relation.

where I' - (13 is the volume of the potential box. The numbe r of states with energy
+
betw(l{!n t; and iI' dlt is obtaincd by diffe rentiating the above cxpression. T his yields
".----
3 112
dN(b') _ 4rV ~; )
(
EII2 dE.

3- --
It is convenient to write dN(b') .. g(J:.1 dE, so that

3 112
'" .. dN .. 4rV(2m) EI 12 2- - - -
g("'I dE 113 (2.19)

is the number of states per unit energy inter"al at the energy E. The function g(b1 is
plotted in Fig. 2- 12. The II.I"CS of II. strip of width dE gives the corresponding number
dN .. g(E, dE of lltates in sueh an cnergy range. The area unde r the eurve from E .. 0
to E .. f gh'cs lhe total number of stales in that energy interval. We llhall have the o I
..
opportunity to use I':q. (2.19) in several problems to appear later in this book. 11"-
~----"ifL----'x -------------

1 ,.) (b)

Fig. 2-1 3. (a) Polential energy of a harmonie oscillator. (b) Energy le\els.

2.6 Th e l'"rmonic 0 8cilln tor

All important physical problem is that. of 0. harmonic oscillator, for which the
dN potential energy is Ep = !kx 2 , as shown in Fig. 2- 13. T his problem provides
important information about atomic vibrations in molecules and solids since, as a
, first ap proximation, we may assume tha t the relative motion of the atoms in mol-
ecules and solids is a harmonic oscillation. SchrOdingcr's equation (2.3) is now
o E

, Fig u re 2-11 Fig . 2-12. Density of energy levels

in a large cubical potential box.
72 QUQ/Ilum mtchani (2.6 Tht harr1l(Jllic OIcilllllor 7J

We shall not attempt to solve this et:IUtltion in a formal way; rather we shall tive
only the main results. Remembering that for a harmonic oscillator w = v'k/m
is the angular frequency, \\'e find thM the possible values of the energy for the
stationary states arc
.-. .-,
E" = (n + !)hw, .-
where II is zero or a positive integer ; tha~ is, tt = 0, 1, 2, 3, ... Thus E" = ;lIw,
.-1
.,
-ihw, ;h4l, etc. The ellergy levels indicated in Fig. 2-13 arc equally spaced by the .-1
amount IIw (or hll, since 11 = 11/ 2:11' and (oj = 2:11''').
All interesting result is that the minimum energy of the harmonic oscillator is
thw or ihll, This is called the zero-point tJltrgy of the oscillator because it cor- .-0 .-0
responds to n = O. This result, like the similar result fo r the potential box, is
closely relat.ed to the uncertainty principle. The classical minimum energy cor-
~ ______*-_________x L-____~------__ x
responds to the point 0 at the bottom of the I>otentiai energy curve. However, at ,
this I>oint we have l: = 0 and also 7) _ O. Because there would be 110 oscillations I' ig. 2- 1-1.Wave functions eorrell(}Qnd- Fig. 2- 15. Probability densitie~ corre-
in such a situation, we would know simultanC!()usly and with absoluto preeisioll ing to the first four energy levels of a har- sponding to the first four energy levels of
both tho position and the momentum of the panicle; this would contradict t he monic O$cillator. a harmonic oscillator.
unccrtninty principle. Therefore the fil'$t energy level or ground s tate should be
the lowest energy level compatible with the uncertainty principle. To sec this, we allll)litude of an oscillator is not sharply defined in quantum mechanics, as it is
note that for this particular level the amplitude:to of the oscillations is very small, in the classical case. I n quantum mechanics the particle may be found at a particu-
and we can make:to ~ till:. Also the amplitude Po of the momentum change is lar instant in a region in which, in the more rigid fonnalism of classical mechanics,
very small and we can make Po - t ilp. The energy of a classical oscillator of itJ! motion is considered to be impossible. There are, however, many experimcnt~
amplitude:to is E = !mw2x~, alld, noting that Po = mw,xo, we have 8uPl>orting this oonclUliion. (We shall discuss them later on.) The probability
dens ity P = !t{x)lf is indicated in Fig. 2-15 for the states corroiponding to the
wave functions shown in Fig. 2-14. Note that, although t he probability of ob-
serving the particle outside the classical limits of oscillation is finite, the particle
The general expression of the wave fUlletions for the simple harmonic oscillator is mainly eonfinc<1 to tho classical region.
will not be given here (see Problem 2.16). Table 2-2 l>rcscnts the fi~t few wave So far we have discussed II. linear oscillator; that is, an oscillator in only aile
functions, with oJ!o eorfl'Sponding to the ground state. Tht'sc functions nrc illus- dimension. In t.he general ease of three dimensions, sueh as the case of an atolll in
trnlc<l in Fig. 2-14. Observe that they do not fall sharply to zero at the classical a solid, the energy levels arc given by
limits of oscillatioll, indicatc<l by the short vertical line in each case. Rather they
extend beyond them, although they decrease very rapidly, as we found previously E. = {n + ;)Aw. (2.22)
for a potcmial stel) in Section 2.4 when B < 8 0 ( Fig. 2-4). This IllCll.ns that the
The only differenoo is that now the zero-point energy is jAw instead of ;Aw, be-
T ABLE 2-2 Wa,e Fu .. e l ion~ or a Harm o n ie Oseil1 a lo r
cause we must add the zero-l>oint energies for oscillations along the X-, and Z- r-,
(1 2 _ ",w/ A) axC8, corresponding to an energy of tflw for each coordinate.

E~ oJ!.(x) F.XAMI' U ,; 2.5. DiscuS!! the l}Qsaible st.ll.tionary states for ~hc l}Qtential energy illus-
" trnted in Fig. 2-16, which is called a 7J(Jltfltial well. This potential energy is defined by
0 ;11'" oJ!O(x) (1i/\/lI")lnt .~~ t'2 Jo:,, '" - Eo for Ixl ~ 0/2 :md 1\. _ 0 for Ixi > 0/2. A potentinl energy of this form has
~I,,,, oJ!L (X) (1I/2\!;) L/22aXt-',tl2 mnny im(}Qrtant a(lplications, e~(Jeeially when Olle is deating with the so-called finite-
2 ;/,,,, oJ!2(Z) (, 8\ ';) 112(4112..f2 _ 2) r 01 "12
range forlX'll; i.e., forces that arc negligible a t distances greater than a certain value called
the rangt, meaning that the patenti!.l is constant outside the range. This situation seems
3 oJ!J(Z) (, 48V;: )II2(8a 3z 3 _ l2az )rol "12
i"'" to be II.llplieahle to the nuclear forces.
 74 Quon/um merhonia (2.6 2.7) \ 75
+(z) .{2
The wave funeliOI1ll for the ground state and the first two e:o.:eited Slatc!;! are shown in
Fig. 2-17 for the case in which three energy le\els are allowed. Note the similarity to
the wave fum::lions for the harmonic osdl1ator. The student should plot the probability
density P _ 1t-12 corresponding to these states; we also lea\e the student to think about
the situation lIhen E > Eo. and to aketeh the wave funclionlJ and probability dcnsiliC!;!.
In this case, all energy values are acceptable and the energy jg not quantized.

E,._ 2.7 Ent!rgy L,!vel8 IImi " ',,,;1' ,.uncllonlf in G encrlll

-{II I ) " " " " - - - -(1)- "
_____ (II }-
Fig. 2- 16. One-dimenaional rectangular
potential well of wid(.h a !l.nd depth En.
Fig. 2-1 7. First Ihre(l wave functions
in a one-dimcnsional potentia] wcll. " the l>article has an energy H, the clu.ssical motion is oscillatory between II and B.
So(u,io", This problem is equivalent to having two mirror_image potential stcPll8O.!pa-
rat~ the di~tanoo /J. CJassic~Il): sileaking, for a negative energy E (that is, f; < 0) the
particle shoukl be confined wlthlll the well; lhat is, the particle should remain between
:z - - 0/ 2 and %, - + .o! 2. lio,,'cvcr. hom our previous c;.:&mples we 8u-peel Ihal in
quant~m mechaniCS thiS 18 not the CASC. For region (1), in which - 0/2 :5 :z :5 0/ 2, the
potential energy is constant and the particle is essentially free, alLhough constrained to
move back and forth. Thus its lield amplitude "'1 (:1:) mugt again be a hannonic function
of type (2.7). Tn the forbidden regions ( II ) snd (III ), the field amplitudes t-2 (Z) and
t-3 (Z) must decay e~ponentially, Jl8 previously indicated in Fig. 2-4 for a single potential
step. There~ore t~e boundary condition used to obtain the .... Ilve funetion of Fig. 2-4
mmt be Ilpplied t .... IOO, onoo Ilt z - -a/2 and onoo at z ~ a12. I3ecause ....e are imposing
t ....o sets of boundary conditions, they can be I!Iltisfied only for certain values of the energy.
Thus the energy E of a particle in a potential .... ell is quantized. The pOSllible values of
E cannot be e~l)ressed in a elosed form and will not be given here (see Exa.mple 2.6 for &
similar case). The number of energy level.'! is limited, being only one, or two, or three,
etc., depending on the depth Eo and the range (1 of the potential. Thllt is, for the case in
.... hich E()II2 < .'f!2/2m, there is only one pOSllible energy level; for
The discussion of the potential step, the l>olentiai box, the harmonic oscillator,
and the potential well suggest the general nature of the stationary stales and wave
functions. ]~igure Z~J 8(a) shows a. potential energy 8,,(1:) similar to that found in
x 0. central force problem or in a diatomic molecule. At large x the potential energy
becomes essentia!iy constant at a. value chosen as the 1-ero of energy, which is the
most USUAl convention. The potential energy decreasc~ as the distance decreases,
indicating an attractive force. At !If the potential energy is a minimum, and is
equal to - Eo; the corresponding distance ro from a is the classical (.'quilibrium
separation. As the distance decreases further, the potential cnergy increases
rapidly, indicating a repulsive force.
For negative energies the motion is clas...iculiy bounded. For example, when
x
These two points nrc called the dauicallimita of ouillaliOI!. For positive energies
(E > 0) such as E' , u particle coming from the right is stopped when it reaches C
and bounces hack, receding to infinity. This is why C is called the da8sicallurnino
pcillt.
W (unOOulld 1l.B~)
~:Dt'fJO'
f(lIltmuum
X ,l-; -O
E,
E,
f--;lr--t-,-;~"E (oound 8tnte) ,

,,2h 2/ 2111 < Boa' < 41f2A2/ 2m , 1\'1

-E
there are two encrgy levels; for
(;,) {Il)
4:r 2A2/ 2m. < E()II2 < 9.- 2A2/ 2m,
Fig. 2-18. (a) General potential energy eurve corresponding to strong repulsion at
there are three, and 80 on. small values of z and negligible interaction at large value!! of;t. (b) Energy levels cor
TC!lI>onding to the potential energy !!hown in (a).
 '.7)
~ EntrgJ ~fI (lnd WfIt'e June/ions in gtntral 77
76 QUall/um mhanic~ (2.7

In <llllllltUIll mechanics the description is basically the same, but certain new
features Il.JlI>ear: (8) The bound stales occur only for cerlain negative energies, so
thaI. for B < 0 there is a discrete 81~ctrum of energy levels or slates. This is tnlc be-
cause, for B < 0, the motion is limited at both classical limiUi of oscillation, thus .>0
imposing /U:(J boundary conditions all the wave (unctions. Hence appropriate
solutiolls of SchnXIinger's C<luntioll exist only for certain energies. This is the same
(l E ... _ O
situation we found, for e.~ample, in the ease of the potential box. (b) Unbound
states c:cist for all positive energics; we then say that, for E > 0, there is a con ;-,ol'lt---------"~;-::O':;;"""'x oJ---~----~-r~-X
li1lUQU8 &1~clrullt of energy levels or states. The reason fo r lhis is that, when E > 0, 8<0
the motion is limited at only onc point, the classical tUmillg point so that only olle
boundary condition is required. Enough flexibility is then left. to allow a sofutioll
of SchrOdinger's C<luation with one arbitrary constant: the ellergy. T his situation "':lc-l-f1rl'-nr--E <0 (loound stJ.\te)
h118 already arisen in the case of the potential step. Physically, the situation ariW)
beCllu$C we can always arbitrarily fix the energy of the purtiele when it is at a
great distance, as we do, for example, when a charged particle is accelcrated in a
machine and thrown against a target. nucle us; or when one atom collides with
another in a gus. (The discrete and continuous energy spectra arc shown schemat- Fig. 2- 20. Rcctangular potential well
F ig. 2-19. Shape of wave functions for
iClll1y in l'ig. 2- 18b.) However, in the case of a potential energy such a.s that limited at:l: _ 0 by a I>otentiai wall.
bound and unbound states corresponding
~ h own in Fig. 2- 1;), corresponding to the harmonic oscillator, the re is no contin- to the potential energy shown in Fig. 2- 18(a).
uous cnergy spectrum and all levels arc discrete.
When the pmticle is in a bound Slate of negative energy E, the minimum
& Iution: First consider the case when E < 0, which oorrt'!!IlQnds to bound states. I n
encrgy that must be supplied to the particle to remove it to a very large distance
euch a case the particle is forced to move classically in the region between :I: - 0 and
is E" = - E. This is called the binding enuyy of the particle in that state. (Some- x _ a, or region (I). The energy E. - -E ill then the di8S0ciation or ~inding eDerg~;
timcs, when we are referring to the ground state of a di9.tomic molecule, we can it I.e., the minimum energy required to remove the particle from the potential ...ell. Sehro-
the (liuocialioll el!uyy, bcc9.usc it is the minimum energy required to separate the dinger'B equation (2.3) for that region, si nce Ep(.z) - - Eo, becomes
two aloms when the molecule is in the ground state. I n the case of an electron in
an atoll1 or molecule, we also call it. the ionization energy.) i'. ,
For R < 0, the wave functions resemble those of the harmonic oscillator, exccpt dJ.2 + k." - 0,
that their exnct. shape depellds on the form of the potential energy E,,(z). Fig-
ure 2-19 shows the wave function for a negative energy level (B < 0) of the dis- where k? _ 2m(Eo + E) l h2 _ 2m(E.'0 - .)/,,2, and Pi - Ilk, is the momentum inside
crete spect rum (a bound state) and the wave function for a positive energy levcl the ...ell. The solution of this equation ill given by Eq. (2.7) or
u: > 0) of the continuous spectrum (an unbound state). Tn both cases the wave "1 (:1:) _ Ae il,. + Be-it;,.
functions extend beyond the classical limits of motion, but decrease very rapidly
outside those limit.:!. In l>articular, for large x, the wave function of a positive Remembering the case of the potential box, we mUilt requirc that 1/11 - 0 at x - 0; this
energy or unbound slAte resembles that. of a free particle and has the asymptotic means that A +
B _ 0 or B - - . 1. ~hus
rorm given by Eq. (2.7),
"l {X) _ A (eil'k _e- ik ,,) _ Csink;:t,
f(x) -;:;;- i\e ih + l3e- ;h,
where C _ 21.1. In region (II ), corresl~nding to:l: > a, SchrOdinger's cquation with
~inee it ll1U~t represent both lhe incoming particle and the outgoing or reflected B ,(:I:) _ 0 becomes
I>:lnicle.
i'.- 01,,
- , - 0,
";X,,' MI'U'; 2.6. Discu~ the energy le"cl~ MId wave functions for the potential el1crgy
des~ribed by thc CUrI'C ~howH in Fig. 2-20..\\ .z - 0 the potential energy goe~ to infinity. where ""
For 0 < :I: < 0, the potential (,Ilcrgy has the cons tant value J-.' - - Eo lind for :I: > (I
it i~ zero. Thu~ it is n u:KtUllrC~ idcalization of the potentilll-(!l1ergy curve of fo'ig. 2- 18.
~p----------------~;---- ..
79
78 QMnium mhon iet (2.7 V)

Whe~. we rcc~lIl.hc discuS!!ion of the potential step in Se<:tion 2.4, we !lee that the s 1 (' The wa\'e functions for the case in whi ch there are three bound states are shO"'n in
of thl$ c<!,uflttOn is 0 U Ion Fig. 2- 21. The student should compare th~ wave functions with thO!le g;."'en for the
potential energy illustrated in Fig. 2- 18. Thus this reiativ('\y aimple example may help
him to better understand our discusaion in eonneetion with the more physicalllOtential
enetgy of Fig. 2-18.
Next we must $ll.tillFy the continuity conditions of the \l'1l"C Funclion at z .. II; that is, Next let us eonsider the positive energy etales (that ie, ""hen E > 0). We note that
they do not eorrespond to bound slates, since a \lartitle may now move between % - 0
ifl .. "'2
and :z; _ <JO. Again using k~ _ 2m(f:o +
R) / ft 2, ~ that p; - Ilk. is the momentum in-
They yield side the well, ,,'e may write the solution for z < 0 as before; that i~,
and k,e cos k,"(l - - alh - " ,
'h (%) .. C sin k;:E.
Dividing these two equiltions to eliminate the constants C flnd D, we obtain For:z; > 0, where E, _ 0, Sehrodinger's equation is now
k;oolk,1l .. - <]0 (2.23) ,
_!!:.... ill/!
. _ IN
or, introducing the expressions for k; and cr, we have , 2m dl;2
where k2 _ 2mE/ ,,2 and p _ 'Ik is the free particle momentum outside the well. The
[2m(li'o - E.)/h)1 ' 2 cot [2m(Eo - 1:'. )/h]l ' 2a ~ - [2mF../f,]1I2. solution to this equation is of lhe type given by Eq. (2.1) . However, in this case it is more
convenient to write it in the equivalent form-
~~ thi,s e(~u(ltion the oU~Y. quantity that has been left Mbitrary so fat is the cnt'rgy I~'."
,I ~Wllt c~prcs...O('s a corJ{hl1o~ rOt,th,1: p~S8iblc energy levels inside the well. However, ~inec l/!~ (%) - D sin (h; + 3).
It 18 Il tran.sccnltcnt~l, equ~tlon! It ~s dlmeul,! to obtain E. in a closed form, as we did for
t~e potentllll IxIx. [he situnlion IS "ery lu milar to tha t described before in connection The quantity" is called the phau .hift; its physical meaning will be esplained shortly.
"Ith the SQuare well (Example 2.5). Thus, depending on the depth I~'o of the well there Applying the eontinuity conditions of the wave function at:z; - a, we obtain
may be none, one, two, etc., lJO<!Sible energy le\c1s. It can be \'erified that if ' (2.24)
k;cotk,a ~ kcot (ka + 3).
Eoa"l < ... 2,,2/8,", ;, This equation differs from Eq. (2.23) in that it contains, among other things, an arbitrary
there is no bound stale; if quantity 3, the phase shif t. Thus we can ",lwaye satisfy Eq. (2.24) for any energy E (or
momentum hk) by properly choosing the phase shift 3; therefore the po!iitive energy

'7/----\-- +---"--.:::::=-" speetrum is eontin uous, as expeeted.

We can understand the origin of the pha8C shift in the follO""ing manner. If the poten-
there is only one bound state; if tial energy "'ere of the ty!1e eoDsidered in fo'ig. 2-6, and shown (reversed) in Fig. 2-22(11.),
the wave function would ha"e been 0/1- lIin b: _ e 1h - ,_ib which eontains the incident
9..- 2/. 2/ 8m < E()42 < 25...2/1'/8,", and reflected beams of particles, both ha\'ing a wavelength), - 'h / k. But when we in-
l)"()duce the potential well (Fig. 2-22b) , the wa\'e fUnction is distorted in the region
there II.I"e 'wo bound slAles, and so on.
0$ x $ a, and, although the wa"elength at :t > a is still 211:/ k, the curve Bin k% must
Thus the number of bound energy levl'ls
be moved along the X-axis the distance 3/ k so that it smootJlly joins with the wave funt-
depends 011 the valuc of the product E()4'.!
lion inside the well at:z; _ a (which has a different wavelength Ai - 2... / .1:,). In other
or energy X (rnnge)2.
words, a local modification of the I>otentiai energy between :t - 0 snd % - a affects the
whole wave function. This is expressed by a phase shift 8 for :z; > (I.

_ We may see that the two forms are equivalent if we rccallthat

;,
e:O.. h kz i siu kx.

o~x
_ COlI

Then
'" _ A,ih+ Be-.h _ ( ..1 + B) cOllh+ i (. 1 - B)sinkz
_ C llin (kz+ 8),
~ig. 2-21. Wave fun ctions correspond-
mg to the JlOlenlial well showli in Fig. 2- 20. II) (ll) where tan 3 - (.-\ + B)/ i ( ..I - B).
 $
80 QU4IItum mWlI.mic, Poltn/wl barrier ptn~lro1iotl 81
(2.8 2.8)
E , ,Jo(;r)
In eident
.. Incident
n.,.."..,
0''--_ _ _ _ _ __ _.,
o --T----Cr-----___-.- -x
E.

, , r'_Sinl;,."
1-- - - 2'1'- - --1 Fig. 2-24. Wave function corresponding to the potential barrier of Fig. 2-23 for an
epergy less than the height of the barrier.

O)r---~--~L O'I"----'l".j~JC_!'-~L/ an energy E < Eo should be reflected back at % = 0, as discuS$Cd before in Sec-
'",,,,,~-,,,-....
tion 2.4 . However, when we consider the problem according to quantuZll mechanics
,,//;
by obtaining the solution of SchrOdinger's equation for regions (I), (ll), and (Ill),
,*,_sin (lizH) we find that the wnve function hM, in general, the form illustrated in Fig. 2-24.
(.) Its components are of the form
(b)

Fig. 2-22. Origin of the phase shift.

where k and a are the same as in Section 2.4; that is, k 2 = 2mE/f&~ and (>"2 =
,,
,(..,)
2m(E a - 8) / f&2. The wave function tl, as in I>revious cases, contains the inci-
dent and the reflected. particlcs; t2 decays exponentially, but it must also contain
the positive e.'(ponential. since the barrier extends only up to ~ = a and the posi-
E
Incident particles tive exponential is not necessarily to be excluded, as it was in the case of the
, potential step. Because t2 is not yet zero at ~ = 0 , the wave function continucs
,
IlcOcclt(1 INlrtieif!ll

- -(I)- J. L ---1-__
.( 111
~=::=;;=:== X
{III) -_ __
=__ TraMmittOO particle!! into region (III) with the oscillating fonn .f3, which represents the transmitted.
particles which have the same energy as the incident particles, but an amplitude
A' which, in general, is different from A. Since.f3 is not zero, there is a finite
probability of finding the particle in region (III ). In other words, it i3 PQlrible for
Fig. 2- 23. a particle to go through the polentiol barrier et-en If 1/3 kinetic energy i3 leu than the
Rectangular potential barrier of width a and height Ea.
height of the potential barrier.
When E > Eo, the classical description of the process indicates that all particles
2.11 /,otentiulllurrier '.f'netrntlon should cross the potential barrier and rcach the right-hand side. H owever, in
quantum mechanics, for the same reason as in the case of the potential step, some
The fact that a wave function Inay extend b d . particles arc reflected at ~ = 0 and at % = a. 1lence the wave functions in the
gives ri~e to an important phenomenon call:;t l:~e/~a.ssl~llimits o.f Illation three regions arc now
us conSider the potential represented in Fi 2-2 en /a ar~ler 7)enetratlOn. ~ct
steps, but in the reverse order of the pot g;. I 3 It c~nslsts of two potential
lft il
potentia/. barrier. As before we shall co cn.d w,e of Fig. 2- 1(i. It is called a
'" tiC ' nSI er t le cases E < g and ' > /' where k;'2 = 2m(E - Eo)/1I2 and Ilk' is the momentum of the particles while they
para e y. lassical mechanics requires that a pace I . ~o ~a
Ie e commg from the left with are crossing the potential barrier.
 Pol~'Jli(J1 borritr JHlttlrolWn 83
82 Quanlwn mt(Mnics (2.8 2.8)

1.0 --- ----7-==-~=~-

f(~)

0.8

, 112 0 ,6
--+"":.."t--+-\f-t,,,,---;<I.-.Prl/~,:::~------- X
1,,j
0.'

0.2
f." ig. 2- 21. Shape of the wa,'e function in lhe general ca.se of a potential barrier.

o , , 7 s
as shown in Fig. 2- 27. We expect, from our previous examples, that. bet.ween A
and B the wave function will be oscillatory, but to the right of B-it must. vary
exponentially. However at C the wave fUllction still has a finite value. Bet-ween
Fig. 2-25. TranSlOiSllion coefficient of II. rectangular potential barrier.
t C aud D, which is a classically allowed region, the wave function becomes oscilla-
tory again. To the right of D the wave function decreases oncc more exponent-ially.
By D.PI)iying lhe boundary conditions at x = 0 and - d Therefore we conclude that there is a finite probability that the particle will be
coefficients 8 C D and A" t f A x - a, we call ctcrmlllC the
' ., III crms 0 both ill the case of E < E .",1 ." " found either between A and B or between C and D. III other words, if the particle
casco.f E >8
It . h 0-
1'1 0
Ie transparency of the barrier is defined as T = IA'12/I A I2
110
is initially between A and B, at a later time it may be between C and D, and con-
~anC8 Wit t,he, energy B, as shown in Fig. 2-25. Kote that for E > B th rd" versely. For this to happen, the particle must ]>elletrate the potential barrier be-
per eel transmISSIon (T "" I) for certain values of EIE h' I 0 C 18
wavelength of the )>article while it is crossing the lVIot.. " I~_~C I. cor~pond to a
tween Band C.
?-/ k' 'h 1 . 1 t'v "II 18 ..... rrlor given by" -
Penetration of a potential barrier has no analog ill classical mechanics because
,\I Ie I IlJ equa to 1\ multiple of ')a Th" ' 'd red - it corresponds to a situation in which a particle has a negative kinetic energy or an
Figure 2- 26 illustratcs a more cnc~i U reso~ance effect.
_ n
IS IS COnsl ,c
if the rmrticle has an cnc ..... v E it g ~. Acoordmg to cla&ncal mechanics, imaginary momentum. This should not present any difficulty in quantum mechan-
may move uct.ween A and B bet C d D ics, however, since we must not insist 011 usillg the logic of classical mechanics in
If the partLcle was initially between A and B it willllever be r~~nd ~~'~ a~
'OJ

d the atomic domain. Barrier penetration h!\.!! been observed in many situations, of
D , and collversc~y. BuL again in quantum mechanics the 10 'e is d'ff "een an
we solve SchrOdlllger's equation for this potential, we I
obta~l W~V:~~I~~t:~~~ which we shall discuss two.
The molecule of ammonia, 1\"H3' is a pyramid with the N atom at the vertex
and the three H atoms at the base, as shown in Fig. 2- 28(a). Obviously the N
t:,.t..~)
Potelltw energy
for N motion

II

S' __ Al
~x
l'otcnti~1
llI1rrier

1\

(. ) (b)

Fig. 2- 28. (a) Inversion molion of the nitrogen atom in the ammonia molecule. (b)
Fig. 2-26. Genera! ease of a potential barrier. Potential energy for the inversion motion.
 Polmlio/ barrier ~ltdroiiolt 85
QUlIlllWl'l muM/tic. (2.8 2.8)

E
Potential energy due to
the IIl'plied eleetric fi~1d
.x . .-.;:--------x

f~-
~
----------
~Jl.lnt

. ";g. 2-29.
(0' (b)
potential cnero'

(a) Potential energy for an electron in a metal ,,-ith no e:..:ternal electric

Fig. 2- 30. Potential energy
version motion in NH3 '- .... _--
,

field. (b) Resultant potential energy when an e:..:ternal electric field is applied.

atom may be at one of the two symmetric equilibrium positions Nand N' on either
side of the btl..'lC of the pyramid. Since both Nand N' must be cqllilibrium posi-
tion.s, the potential energy for the motion of the N atom along the axis of the
pyramid must have two minima and have the symmetric shape indicated in
F ig. 2-28(b), with a potential barrier between Nand N ' . If the ~ atom is init.ially \
at N , it may eventually leak through the potential barrier and apl~r aL N ' . If
the energy of this molion is 1e811 than the height of the l>otential barrier, such as State Is
the energy level E in the figure, the motion of the ~ atom is coml>OSt.-d of an oscil-
latory motion between Il and S or between T and U, depending on which side of
the plane it. happens to be, plus a much slower oscillatory motion between the two
classical regions passing through the l>otential barrier. The frequency of this second
motion is 2.3786 X IO lo H7, for the ground state of XH 3 . It is this second type of
motion which we usc to define a time standard with atomic clocks.
A s another e:..:ample, let us consider the case of the electrons in a metal. Their
potential energy is shown ill Fig. 2- 29(a). If an electrou at the highest l.!nergy level
is to escape from thl.! metal, all amount of energy at least equal to.;.o must be sup-
plied to the electron. This amount of energy may be provided by heating the metal
or by the absorption of n I>hoton (as in the photoelectric effect). But. the electron
may also escape if one applies an exteMlal electric field whose potential is shown by
the dashed straight line in pig. 2- 29(b). The resultant l>otential energy is illus-
trated by the solid line in Fig. 2-29(b), and is equivalent to a l>otcntial barrier.
The most energetic electrons in the metal can leak out through the barrier, rcsult-
ing in what is cnl1cdfield electrOIl emiuioll. In Section 8.:~, we shall discuss another State 0.
barrier penetratiou ellect, the emission of alpha particles by nuclei.
,,"----- ----... ---
EXA MI'I"#!: 2.7. Alll\lysis of wave function ~ and energy levels for the inversion motion
of ni trogen in the N II 3 molecule.

50/11 /,;0.0: To show how much uscful information we can derive from a qualitative
analysis of the WIII'e fun ctions, we shall 1101" discuss the in,"eTl!ion mol..ion of nitrogen in
_-==-___-..::::.t;:------,----- ---ix
the NHa molecule in more delail. Figure 2- 30 reproduces the rmtential energy shol' II in Fig. 2- 31. Wave functions eorreslmnding to the four lowest energy levels of the inver-
Fig.2- 28(b). t el us look M this potential energy as if it were the potential energy of a sion motion in i'H3.
 86 (2.8 2.8) PoUnliol barri~r ptnelroliol! 87

\ . I
0

0
\
"
'" /
e,cm-' \ J " / 0.2 E,eV
&aklt
... I- \ ~\ / 0.1

X 0.8
"-0.' '"0 0'< 0.'
o
r-0.76 A
..... " Fig. 2-33. Energy levels for the inversion motion in Nlia .

I vels are shown in Fig 2- 33 where the llUffiocrs correspond to the energy leV(~ls of the
X
~ I-I molecule The height of the potcntial barrier in NI13 is about 0.254 cV. The figure
~ .. I"
) \;so 3~hows tha~ the separation between the pair of level-! 0$ alld 011 corre.sponding to wave
~ul\etious 1/10 and ~ l or between the pllir of leveb 1$ and III correspondlllg to wave .func-
tions ~~ and 1/13 is very small compared with the eel)f\ration ~t\\"e?~1 the two pairs of
cnergy levels. Table 2-3 gives the first eight energy l~vel~ of Nih I he symbol used to
designate each level will be explained in the next ~eetlOli.
X
TABLE 2- 3 Vihra1ion,, 1 Energy l..eocls
for A ~;a l i'\ I Olion of N ,\ Iom
Fig. 2-32. Probability densities corresponding to the ",a,-c functions shown in Fig. 2-31. in N 1I3 Mot ec ul e Rcilltio'e
10 the Gro und S late
simple harmonic oscillator with a bump or barrier at the center. The effect of this central
bump is. perturbation that affect.! the motion of the particie, mainly &.'! it P&MeS through Level ,m " .v
the center. Ae indicated before, this effect-for particles with energies such ILS E, f1mallcr
3a 2861 0.3547
than the height of the potential barrier-is to decrease the probability of finding the
2J8O 0.2950
particle in the central region. We can translate this into quantum-mechanical language
by saying that the bump distortl! the wave functions of the harmonic oscill&1or potential "'" 1910
1597.4
0.2367
0.1980
in the central region, decre&lling their amplitude in that region. Figure 2-31 show! the
"..
first four wave functions for the harmonic oscillator potential without the bump as dashed
linea. The actual wave fun etion~, when the effect of the central barrier is taken into
account, are shown as solid lines. Figure 2-32 indicates the eorre!lponding probability
denllitiel!, I-(:z;)12.
.
I.

O.
986.00
950.16
0.79
0.00
0.1222
0.1178
9.84 X 10- 5
O.
An analysis of the!\C probability deMities shows that l-ol2 and I ~II~ are almost identical.
.. The unitcm-' will be defined in Section 3.3.
The main difference is that I-ol~ represents a slightly greater probability of findillg the
It is equivalent to 1 eV - 8067.5 ern-I
particle within the potential barrier than l-d 2. Therefore the energies '0 and EI of tho
corresponding stationary states must be almost equal. The same happens for I ~ ~I~ and
2
14'31 , although the silnilarity of these two wave functions is lIot as close as for -o and ~I. The 1I100t important result to be derived from this csample i~ that when we have t\~'O
Th u.s the energy levels E2 and I:.'a must also be very clooe, but not as c]~e as Ho and potential wells scpurll.ted by a potential barrier, the low('r enerlty levels arc :ro;J~ In
El. However, for ellcrgies greater than the height of the central barrier lsuch as 1:." in closely related pairs, or doublets. If we hal'e three wells instead of two, \\"~ S OU mv;
Fig. 2-30), the hindering effect of the barrier is greatly reduced and thc wave functions triplets of closely associated Cllcrgy lel'el~, and so on . .\ JI we 8hll.~1 see l!loter ( III Chapters
and energy levels arc essentially the same as those of the harmonic oscillator. The energy and 6), this is vcry important in the study of moleclll('~ and solids.
88 Quantum muhaniu
(., (b)
Fig. 2-31. Symmetrical mOlions: (a) pendulum, (b) planetary orbit.
2 .9 S fJ'''In t!lr"~ ' Vu r::f.! F"n c(ionN~ and l*trrUII
Considerations of symmetry are often a great help to the physicist who wishes to
obtain certain kinds of useful in formation witho ut having to perform actual cal-
culations. For example, in the motio n of a pendulum (or in any simple harmonic
motio n), the position of equilibrium 0 (Fig. 2-348) is a center of symmetry. T here-
fore when th~ pendulum is at symmetric positions, such as A and .1', its velocity
and acceleration muat be the same in magnitude; the time required to move be-
tween A and 0 must be the same as the time to move between A' and O' the
change in velocity, or in kinetic energy, or in potential energy in going from to
o should be the same as that from A' to 0, and so on. In the case of planetary
motion (Fig. 2- 34b), line PQ is an a.xis of symmetry of the orbit and therefore the
velocity and acceleration of a planet at symmetric positions .4 and A I must be
the same in magnitude. the times to go from A to P and from P to A' must be the
same, and so on. Jn gencral, if the potential energy is symmetric relative to a certain
point, such as 0 ( Fig. 2-35), we know that when the body is at symmetric positioll8,
such as A and A', the dynamical conditions must be the same.
In quantum mechanics, considerations of symmetry are even more useful and
important than they are in classical mechanics. For example, when the problem is
such that the potential energy has a center of symmetry, requi ring that the particle
4<-----i---+-"
Fig. 2-35. Symmetric potential energy.
--'---f,,',-'--A!----~Oi--A+',...'-oIi~.....,X
2.9) Symmdry, wfwejuIJdions, olld JXl1'ily 89
be in the same dynamical state at symmetric positions, the probability of finding
the particle at these symmetric positions Illust be the same. Since this probability
is given by 1ol2, we conclude that if A and A' are two positions, symmetric relative
to lile center of symmetry of the physical problem, as in Fig. 2- 35, then
(2.25)
T hat is, if we plot 1o12, the graph should be symmetric relative to thc center of
symmelry. Now, assuming that the wave functions arc real, Eq. (2.25) requires
that
(2.26)
T herefore the wave function at symmetric I>oints must. be C<lual in rnagnit.ude but.
may be Ol>posite in sign. When Oil = +>1-,1', we say that the wave function has
even parity. When oJtll = -oJtll" the wave function has odd TJarity.
In general, parity refers to the behavior of the wave function when evaluated at
two symmetric positions. We conclude then that
for problems hailing a center of aymmctry, Ihe s/aliQ/!ary s/ales are de-
scribed by ualle juncliolls iwvillg a u:ell-<leji.1!ed 1larily, ellen or odd.
Let us see how this important. conclusion nl>plies to the problems we have con-
A sidered previously. I n the potential box of Fig. 2- 6, the I>oint x = a/ 2 is a center
of symmetry; thus the wave functiOllS must be even or odd relative to x = a/ Z.
We can see this clearly in Fig. 2-8(a), SO tha(, we may say that states with n = I,
3, 5, ... have even parity while those with n = 2, 4, 6, . .. have odd parity. The
probability distributions, illustrated in Fig. 2-8{b), satisfy thc re<luirement stated
in Eq. (2.25), being symmetric relative to x = 4/ 2.
For the case of the hannonic oscillator, the center of symmetry is x = 0
(Fig. 2- 13), and the wave functions for n = 0,2, 4, ... have even parity, while those
for II = 1,3,5, ... havcodd parity (Fig. 2- 14). The Jlrobability distribution for all
stationary states is symmetric relative to x : : I 0 ( Fig. 2- 15).
We used this principle of symmetry implicitly when we discussed the wave func-
tions fo r the potential well (Fig. 2- (6), which has a center of symmetry at x = O.
However, the potential energy considere<1 ill Example 2.G does not exhibit any sym-
metry Wig. 2-20), and the corresponding wave functions arc neither evcn nor odd
( Fig. 2- 21).
The I>otentiai energy fo r the inversion motion of the N atom in the KH3 mole-
cule, discussed in Example 2.7 (see Fig. 2- 30), also has a center of symmetry, and
the eorresl>OlI(ling wave functions ( Fig. 2- 3\) arc even or odd. The even or sym-
metric wave functions arc designated by 8 and the odd or antisymmetric ones by a.
In T able 2-3, successive even and odd wave functions nrc dCllignated Os, Oa, Is, la,
etc.
Another interesting fact, which we mention in passing and which one may
gather by look ing at Figs. 2-8, 2- 11, 2- 17, and Z~3\, is that the wave fU11ction of
the ground state always has the same sign (in the language of algebm, we may say
9Q QU(ltllW11 mh(llliu (2. 10 9J
2. 10)

that the wave function of the ground state Il(u flO roollJ), while the wave functions related to thc fact that the energy of the partiele depends Oil the square of the
for the first, second, third, ... excited stales cross the axis (or change sign) ollce, momentum through the relation E = p~/211l +
t:,(x). .
twice, three times, ... (or have one, two, three, ... roots), Thus we may conclude Next we shall try to obtain a solution of Eq. (2.27) which is ad<''CJ.uate to describe
that stationary states. From our knowledge of standing waves, we may assume that
the more lime' iJle u.'(U)cjlmcliQn chan{#JI sign (or the grtaler the numbtr such' a solution must have the position and time variables separated. We shall
of Tool .. ), the grcaler the energy of the corre8ponding 8lationary &tale. try a solution of the form
"' (x, t) = .y(x)e-it:1 -. (2.28)
~

2.111 The TI", e .',pppnt',nt S.:hrofllngcr Eqllatlon Next we must I)rove that E is the ellergy and >/-(x) is the amplitude satisfying
So far we have discussed only the SI)RCC distribution of the maUer field, a!l(r have Eq. (2.3). T o see this we note that
cOllllmtcd its amplitude or wave function .y(z). Nothing has heeu said about the
lime variation of the field. T o discuss time dependence, we must have an equation and
containing the time; this C(llUltion is called Sclmxlinger', time.defMndent equation.
I t plays a role in quantum mechanics similar to i\l axwell's equations in electro- Substitllling these two expressions in Eq. (2.27) and canceling the common factor
magnetism. Schrodinger's timc-dependent equation is: e-diI /A, we obtain Eq. (2.3) for >/-(x), and therefore E' must be the total energy of
the system. T herefore the malter field given by E(I. (2.28) olScillates with all angular
frC<juency
(2.27)
w = El h E = flw = III},

where we now write "' (x, I) instead of >/-(x) for the wave fUllction, so that we in-
clude both time and space dependence. We see that this equation for the matter
field, "' (x, 1), differs radically from the wave equation iJ~~jOt~ = 1/ 2 a 2 UiJx 2 , which
describcs claatie or electromagnetic waves, because it contains only the first-order
time derivative iJVtjOl and not the sccond-order time derivative. In a sense
Eq. (2.27) resembles the equation for transport phenomena, iJUal = a 2 a2~/ax~,
which is also of first order in the time derivative and describes heat conduction and
diffusion. However, there is again an iml>ortant difference: the imaginary factor
i = v=r, which multiplies the time derivative in SchrOdinger's equation. There-
fore the field described by Eq. (2.27) is different from elastic or electromagnetic
wa,'cs 011 the one hand and diffusion or thennal waves 011 the other. " 'e must re-
frain from tarrying the analogy betwccn quautum-mechanical fields and clastic
and electromagnetic waves too far.
1\ote that we ha\'e only written down Schrodinger's time-dependent equation
and have not derived it in the same way that we can establish the wave equation
for clastic waves in a string or fo r electromagnetic waves, starting from morc basic
principles. We could now say that Eq. (2.27) is a fundamental law of nature, in
the same way as the Faraday-Henry law of electromagnetic induction or the prin-
Ci l)le of conservation of momenWm arc fundamental laws of nature, and that its
mathematical form is the result of a careful analysis of cxperimental facts and in~
in acco rdance with Eqs. (1.44) and ( 1.45). As indicated before, the field expressed
by Eq. (2.28) is typical of standing waves becau$C the space alld tilile parts are
ineluded in different fsctors. However, the iml>or(allt difference, when oompared
with standing waves all strings, in air colUlllns, or in metallic caviti~: is that the
.
time part cannot be WTlLten . wi. or cos w,I b
as sm U tonly...."
"D e-'..I _ e- '.!;I / .I ' and this
is because Eq. (2.27) is of first onler ill time. That iii, quantUlu-mechalllcal waves
always ha,'e a complex time dependence.
(o'or a free. particle moving in the + X-dircction with momentum p = flk, we
have >/-(x) = .4e ik .<. Thus the time-depcndcnt wave function is
(2.29)
which desc ribes a wave propagating in the + X-direetion with a phase velocity
v. = wl k = Rip = ~v, a.s we discussed in Section 1.11. This corroborates the
statement made in Seetion 2.3 that the wsve function >/-(x) = e>k.r oorresl>onds to a
particle moving in the + X -direction. Similarly, the time-dependent wave function
corresponding to >/-{x) = e- ih is "' (x, t) = At-,('h+,,'), which describes n. wave
propagating in the negative X-direction. However, we cannot use c~ (kx - wt)
or sin (kx - wi) instead of Eq. (2.2!l) to express -V ex, t) for a free partIcle, becallse
these functions are not solutions of E<I. (2.27).

.
For a particle in a. potential box,
tuitive thought. This statement is essentially correct. H owever, we call in fac t
obtain Schrodinger's equation if we start from certain basic ass umptions. This is . n"lf"x 11 (ei~"'/o _ e-i"u/ o)
done in the formal theory of quantum mechanics, whose discussion is beyond this >/-(x) = AsUl --~ 2',
book ; however, Sectiol"' 2.12 docs give an introductory analysis. We may Iloint. out
he re that the fact that Schrodinger's timc-depcndent equation is of first order in
the time derivative and of seeond order in the ~ition derivative may be directly
92 Quail/urn fflt('Mnics (2.10 Thl linu4tIHlldmi &hrQdinger tqualion 93
2.10)

This equation corresponds to two waves traveling in opposite directions which
result. in standing wavcs, as in the case of a vibrating string with fixed ends.
A solution of the form given by Eq. (2.28) describes a particle moving wilh a
well-defined energy, corresponding to onc of the energy levels or stationary slates.
In this ease,
(2.30)
so that the probability density I+(]:, t)12 is independent of time. This is why states
described by Eq. (2.28) were previollsly designated as""8lali(mary. We must. lIote,
however, that Eq. (2.28) is not the only solution of Eq. (2.27), and that other
solutions exist for which 1+(%, t)12 is 1101. independent of time. The corresponding
states are not stationa ry. Using a result from the theory of differential equations,
we can express the general solution of Eq. (Z.27), corresponding to nonstationary
states, as a linear combination of stationary-statc sohltiolls; that. is,
the state describ......,j by the given 4x, t) is not stationary. This result gives us a
clearer idea of tqe difference bctween stationary and n~nsta~ionary 8ta~es. Although
for stationary states liI(x, t)1 2 is independent of lime, III nonstatlonary states
1+(.:1;, f)12 contains a series of oscillal.ory terms with .frequeneies v = .(E~ - E,.:>!h.
The wave fWlction given by Eq. (2.32) may describe a syste~l dunng a lra.n:'ltio.n
between stationary states 8 1 and E 2 . If the particle 8ufTenng the translt.lon IS
charged, we may say that during the transition the particle ~haves 88 an OSClllal.or
having a frequency given by Bohr's equation (1.29), v = .{E I --:- e.2)/h, and there-
fore is capable of emitting or absorbing electromagnetic rruhatlon of the same
frequency. Hence the formalism of quantum mechanics incorporates Bohr's equa-
tion EI - E2 = hv in a natural way.
EXAMPtE 2.8. Discussion of the wave function descrihillg the inversion of the NH3
molecule.

-V ex, t) = I: c,, >Jt~(x)e-iE.I/ ~. (2.31)

"
(This is sim ilar to the Fourier analy~is of a wave.) The above eXI>tcssion of "'(x, t)
is a solution of Eq. (2.27), as we may verify by noting tha~ each term, being of the
type given in Eq. (2.28), is a solution of Eq. (2.27), and that their sum is also a
solution, since k:q. (2.27) is a linear homogeneous differential equation. Fig. 2- 36. Description of the inversion
As a more oonercte illustration, let \IS consider the case in which 4'(x, t) can be motion in NH3 by mellll~ of time-<iependent
expressed as the sum of two stationary terms; that is, wave hmction~.

(2.32)
o
To obtain the initial wave function, we set t = 0, resulting in
Soh,lio n ' Suppo!;e that the N atom is initially (moet Ilrobably) i~ the right potential
well ground state (see Fig. 2-30). Therefore the initial wave fUDctlon .mUllt be large at
the right well and very small at the left well. The initial wave funcuon then may be
We can ooll1l)Ute the coefficien ts Cl and C2 by a straightforward mathematical e:oqll1,'ssOO lI.8
method if we kllOw 4'(x, 0) (see Problem 2.37). H ence we can determine 4' (x, I) if
we know the initial wave function 4'(x, 0). '1' (%,0) - "'/l,
The probability distribution corresponding to 4' (x, t) is and it hll.8 been represented in Fig. 2-36(81). Recalling the shape of the fU!lctions >Jto and
>Jtl in Fig. 2-31, we may also write, as a good appro:o:imlltioll,

The wave fUlIction after 110 certain time t is given by

(2.33)
Setting t:..E _ El ~ Eo, we can write this c)(pression as
Thus P{x, t) is not constant, but contains tcrms that oscillatc with the angular
frequency W"'" (BI - B 2 )/1i or the linear frequency v = (E\ - E 2 )/h. Therefore
9ft (2. 11 2.11) TNlII,ilioll probahililia and ui/ion rille' 95

,\t a time t _ -rfl/IlE, the eXllOllcnt in the parentheses is -I, and "'e have
"'(x, I) - (Y,o - y,1 )e-'.II. - '111ft-l/oll.,
where, from the shapes ofy,o and y,J as shown in Fig. 2-31, we see that ilL" y,o - 0/11
is conoentrl\led on the left. This i!!allW !!hown in Fig. 2-36. Therefore the particle-the
N atom ill our examlllc-is (most Ilrobably) ill the left potential ,,'1'11. In other words,
the NH3 molecule has beell illvcrted. Obviow;ly at a lime t _ 2d/Il";, the l)artieie is
again baek 011 the right. Therefore the frequency of inversion of the molecule is gi\"en by
~ - IlR/ 2-r/, _ (RI - ":o)/ h. The eXIJI'rimental value for po is 2.38 X 10 10 H ~, from
which we can calculate the enerJt.v difference EJ - Eo as 9.84 X 1O- 5 eV. This is the
value given in Table 2-3.
2.11 Tr"nlCllion ,,..",,,llIlItl..,, and Selection lIul"lI
It is logical that at this moment the studen t should ask the following qUClltion:
HoII' can quantum mechnnics Inedict u:hen a transition is going to occur? In other
words, if an atom, molocule, or nucleus is in an excited state, how may we know
when and where it is going to jump to a slate of lower energy? Or if the atom,
moloculc, or nucleus is sllbjoct to an extemal eloctromagnctic field, how may we
determin(l whether it a bsorbs energy and passes to an excited state? The answer
to these questions is that we cannot tell the exact time at which th(l tmnsition will
take place, but that fo r each jUmp, let us say from state i to state f, the re is a
tral!sitioll llrobability pe r unit time, T,,, which we can compute according to the
lawll of quantum m(lChanies and th(l interactions responsible for the transition. The
largl'r Til! the more likely it is that the t ransition will occur. Of course, if Til "'" 0 ,
the transition is impossible or forbidckl!. This result implies that not all transitions
which saUsfy Bohr's equation, /I = (E' - E)/h, are possible, because, in addition
to the conservation of energy, other considerations enler into the process:. Angular
momentum , for example, must be conserved. Also, because of the Simce symmetry
of the system (thaI. is, the parity of the wave functions), it may not be possible for
the waye function of the initial slate to undergo an adjustment so that it will be
tmnsfonnoo inlo the wave function of the final state by a proper mdiative process..
This limitation in the possibl(l transitions gives rise to ul~clj(m rul~8. These rules
state whieh arc the mol"<' Ilrolmble or allott-ed tmnsitions; i.(l., for which the tmnsi-
tiol1 prolmbilities have large values.
During an eloctromagnctic transition, the system may behave as all oscillatinp;
electric o r magnetic mullipoie, and therefore we have electric or magnetic dil>ole,
QSCillator is dilTe rent from zero only if
(2.34)
wJ(erc dll = "I - tl" which gives. th(l sdoction nile for the first.-order allowed
tmllsitions of the oscillator. This menns that the first.-onler allowed transitions of
11 harmonic oscillator arc from one neighboring state to another; i.e., from a state
whose quantum number 11 dilTers from its neighbor's by I . Thus the energy
absorbed (Ill! = + 1) or emitted (61\ = - I) in Oll(l transition, according to
Eq. (2.21), is
(2.35)
where v is Lhe frequency of the harmonic oscillator. Comparing Eqs. (2.3.') with
Bohr's C<ttULtion, wc sec that the harmonic oscillator can emiL or absorb radiation
of only one frequency, which is equal to its own (the classical o>\Cillatory frC<lucncy)
und so its spectrum i~ limited to only olle freqrnl\cy.
When a ~ystcm is in an cxcitl'(l ~ta le it will remain in lhe exci tcd stale for only
a certain length of time bccau.;;e of the probability of its jumping into a low(lr
energy level. T he averlllJfl lifetime of 1111 excited state is invel"3Cly prol>ortional to
the total transi tion probabililY of that state; i.c., the sum of the probabiliiies. of
til(! transitions 10 all the low('r cllerg)' levels into which it may jump. The lifetime
of the groulld stale of an isolat(J i<YRt(lm is obviously infinite, since the system
cannot jum l) into a lower level. I.ifetimes. for allowed atomic and molocular lmn-
sitiolls arc of the order of 10- 8 s, while the lifetimes. for nucJctlr transitions range
from 10-8 to 10- 14 s.
Although transilions in which n systt'1Il in an excited stale emits ellcrgy by
jumping to a state of lower ell<'rgy may occur ISI>ontnnrously, it is nC<:(lS.."~uy, if a
s.r~lem is to absorb energy, (or an extcnlal action to intervene. If the sy~tcm is
initial\y in an exeitro stale, thi8 external action may also induc(l emission of energy,
in addition to the I'I>ontanooll]j energy cmis..~ioll lUI a remit of the perturbation
produced in the system. This i;j called $limula/ed emiuioll, and is vel)' imporlant
in many cases. Th(l three proccs..~absorption, ~ I)Ontancous emission, and stimu-
lated emission-arc illll~trntcd in Fig. 2- 37. In Example 1:1.\ we shall obtain the
relation betwl.'"Cn the SI>ont:mcous lind stimulated transition I)robabilities..
[nit~t1 Fin,,! Initi~t Filwl Inilia! Final

;:T ~~
st~tc 8ta te ~t"t.. 'I"t~
quadrupole, etc., tmnsitions, each characterized by its own transition probabi1i!y
and sdeetion rules" Ullually the mOllt probable transition ill the electric dipole, fol-
iOW(ld by the magnetic dipole and the doctrie quadrupole. Higher-ordcr multipole f:'~~
transitions ha ve very small t mnsition probabilities and are, in general, disregarded
exeep~ for some spocial CIlJ!CS in nuclei. Transitions for which the eloctric-dipole
transition probabilily is not zero arc called fir8(-()rd~r allowed. When the (llectrie-
f,.,J ---
(a ) .\1.o:<orplion
HI--
!hl
~

~1)()nln"<'Ou~
HI--
(e) :-:\unu!nted
dipole-transil ion probability is zero, the t ransition is called jirsl-order forbidden, cm,8SOOU emi!!!!"'n
even though such II. transition might still occur at a much lower mte, as a mag- Fig. 2-3i. lbdi:ttil"c \lroct'~"('s: (1\) ab!<OTJltion; an incident Ilholol1 is ab~orbed; (b)
netic dil>ole or an cloctric (Iuadnll>ole transition (or even a higher-order mullipole Spontnlleolls emi,,<;ion. re.< ullin!! in II photon; (c) stimulated emis."'ion under the action
transition). For examl)lc, !lIe clc<:tric-dil>o]e t.ransition probability of a harmonic or an incident photon.
96 The jormlJllhtory of qU(ln/um muh(lfliCI 97
(2. 12 2. 12)

2.J2 Th,' "orlllal Theorg of tlllant"nt lflechan;ctl
Thus far we have developed a quall~um theory for atomic systeOls based on
SchrOdingcr's et:lustion. With the aid of the wave functions resulting from the
solution of Schrodingcr's equation, we call obtain information about the possible
energy levels of the system, the probability of finding the system at a particular
region of space, the I>robability of a transition from one energy level to another,
the frequency of the electromagnetic radiation emitted or absorbed, and 80 on.
However, so far it would seem that the only information we can extract from the
Jaws of quantum mechanics concerns the energy of the system. This is not so.
H is posaiblc to express the principles of quantum mechanics in a formal way,
which makes it possible for us to obtain all the necessary information about a
physical system. We shall now I>rcsent, in II. simplified way, this [omlal theory.
Consider first the onc-dimensional problem. SchrOdinger's equation (2.3) can
be written in the form
(2.36)
When we wrote the left-hand s ide, we factored out the wave function f(x) M if i~
wcre II. common factor of the (Iuantities inside the bracket. However, each term
in the bracket Illust act on, or operate on, f (x) according to its own nature. T hat
is, Ep(x) multiplies f(x) but d'l/dx~ produces the second derivative of f(x). In
mathenlllticallanguage we may $4y that the expression
H ... 2m. ' ( dx2d') + Ep{x)
_f/
2
(2,37)
There are in general, a series of Ilwper values a" a2, 0.3. ' .. and a serics of associ-
ated prol~r functions -Ir -2. h, , .. , wl~i~h del>;nd on the nature ~f the opcralO~
and on \he mathematical boundary conditions. rh(!!(C proper fuuchons are a con
sequence of the physical propertics of the system. In some cascs there arc several
wave functions corresponding to a given I>ropcr value; in that case, the proper value
is said to be liegellerau. ..
In quantum mcchauics the oJ)<'rators belong to a class called l~eml!llOlI (Ila.~ed
afte r the French m.athenlRtieian C. Il ermile), These opera tON s:lt Isfy the Condillon
J<I>~A<I>zdT= J!A<f>2J<f>ldT (2.-10)
fo r all functions <1>, and <1> 2 which satisfy the required boundary Cllllditions. It can
be shown that
the proper ~'a[ue8 oj hermitiall operator& are reat a/I(/ that their proper
Junctio/18 are QrlilOgo/Jai.
T hat. is,
(2.-11 )
where l/;; and -j are proper functions belonging to proper values a, an(~ a, of A.
T he operator H given by Eq, (2.37) plays a very important role .In quantum
Illcchanics and is called the hamillOlliali opera/or of the system. In el~sslcal mechan-
ics the total energy is callc<1 the hamihonian when it is es:pr~11II te~ms ~f the
momentum and the cOO.umalCS_,' 0 " lIe sys t em. 1'"0' v ,0"
,>article movlIIg III one
direction the classical hamiltonian is

appearing inside the brackets is an operator", which, when it acts on a function Hd ... ; 1 = 2~ rl + E'~(x). (2.-12)

f(x) (that is, Hf(z, produces a new function as II. result of a series of mathe-
We may correlate the classical a nd quantum-mechanical hamiltonians ill a very
rnalieal operations explicitly COIIUlined in the definition of H. In particular
simple way, By comparing E<is. (2.37) and (2.42), we sec th~t w~ may transform
Eq. (2.36) call be writtell in the symbolic [oml,
the classical hamiltonian into the cluantum-lll<!Chanical hamlhoman operator by
Hf (z) = Ey,(x), (2,38) making the correspondence

which mcans that the effect of H 011 -(x) is to multiply -(x) by the constant E. 'k d (2.-13)
p'" -l d.e
Obviously when H operates on an arbitrary function the result is 110t II<!CCSSIlrily
the same function multipl ied by a constant, but ill general it is another, different !T he minus sign in Eq. (2..13) is only a mntte r of convenience.] For motion in three
function. Those functions satisfying Eq. (2.38) are called the proper JuneliQ)!& of dimensions, the clMSica\ hamiltonian is
the operator H, and the corresponding values of E are the proper ~'alue& of the
operator.
1:1 <1".;0.1
1 I' 2
= 2n~ + I-'-'~,
(r) (2.14)
For an a rbitrary operator A, the proper functions alld the proper values are
those satisfying the CC\WLtion ,
where r is the position vcctor of the particle and p = pz , '+'
111 + P.,
' The logical
Ao/;{:t) = ay,(:t), extension of the correspondence expressed by Eq. (2.43) is
(2,39)

Operators will be designated by aans-scrif symbols. P - ! - - I'h'

ax
-, Pr ..... - t'h -'
ay , P
.-!- -~

"
_
'. a
. (2.-15)
 98 2.12) The formailht'Or)' of qUll1l/UnI I1UI:halliu 99
(2./2

Using the vector OIX!ro.tor V, read del, defined by TAHLE 2- -1 Quantum O I)C ~a to r8

v "'" II .-+ U.ay

z
J:
U-"dz,
-+ Quantity Cla".,icsl definition Quantum operator

Po.;ition , ,
we may write E(I. (2.45) in the morc compact fon}l, :\Iomentum - iftV
I'
.\ngular momentum >Xp -illr x V
I} ...... - iAV.
(2.46) Kinetic energy ,,'! 2111 -( A'l2m)V"l

Replacing p ,ill the clWlSical hamiltonian by the operator -ih fl, we get the quail.
Total energy p7 2m + ,.: .(r) _(II' 2111 )9 7 + ":.{r)
tum-mechanIcal ol>Crt1tor

- 2m V .'
, + E,,( r )
"(a 2 a2 (J2 )
In this way we may dctennine thc values not ollly of the cnergy but of any other
I>hysical quantity. Thi:s principle, tll(!reforc, tells us what physical information
we may extract concerning a system. Slating the I>rinciple in mathematical terms,
we may set up the operator equation
::3 - 2m ax2 + ay2 + iJz2 + Ep(r), (2.47)

OI}Crating with H on II. fUllction .p(r ), we have

A(r, - ill V)" = a". (2,48)

Next we shall find the po:ssib\e \'alucs of a and the functio ns " that satisfy this
_
Hofer ) - -
.' (o2y, a2", 02",)
2m dx2 + ay2 + dz2 + Eper)"'.
dilTerential equation with the required boundary conditions. Thc propcr values
aI , a 2, a3, ... arc the only possible result.s of a mcru;urcmellt of .1. We also say that
~~ !/8 a prol)er function of H, we ha ve H", = 4-, where E is tilll proper value of the proper functions "I, "2. "3,... describe the I>ossibie states of the system insofar
as the physical quantity A is eoncern(!{\.
Z Obvimlsly if the system is in a stale described by the proper function ,,~ cor-
.' (02){1
- 2m ax2 + a'", a ",)
ay' + dz' + Ep(r)!/- = BY,.
responding to the operator A, then the valuc of thc physical quantity A is a~.
But what happcns if the system is in a state described by a function <I> whieh is
none Gf the '1-. solutions of Eq. (2.48)? In such a case, we say that A docs not have
T his is just Schriklinger's equation in three dimensions, as stated in Eq. (2.9), and
a precise vallie. Expanding the wave function <I> in (emlS of the proper fUllctions
therefore we may ,MY. that Eq. (2.47) gives the quantwn-mechanical hamiltonian
operator of a partleie In three dimensions. y,,, of thc operator A, we obtain
On l?C basis of relation (2.'16), we may slate the jir8t principle of quantum
mechalllc" a.s follows:
Whcn the functions y,,. are orthogonal, then obviously
J: To et'er" phYllicaJ. quantity A(r , p ), u'hich i, a fundion of the POI;""
/10'1 ~lId momentu~l of a parti~le, tMre corre,po'ftds a quantum olM ratQr, (2,49)
Dbtallled by repiaclll9 p by -,hV,. that ill, A(r, -ihV).

Thercfo~ thc hamiltonian ol>erators (2.37) or (2.47) arc the quantum to
correspond n t th t ( I opera NI
. . I ~ 0 c. o.a energy of the system for motion in one and thrcc dimen-
SIons, n:specllvelY:i Slmll~ r!y, to the kinetic energy E" = p'/2m, there corresponds
t~e operator -(h 12m)V III three dimensions, or -(h~/2m)cl2Idc2 in one (limCII-
81On. Table 2-4 ~un.lmarizes the quantum operators for severall>hysical quantities.
The tecolld prmelple of quantum. median ie, statcs:
J .r. The ollly.po88ible t'alue8 that call be obtabud when a phYltieal quan-
illy A (~, p ) 11 meaBUreri are Ihe J1roper t'alue8 of Ih e quallium operalor
A(r, - lhV).
T herefore the /iJird prillciple of quaIl/lUll mechanic' s ta testhllt
I II. When Ihe h/ate 0/ the syslem correhpol/ds 10 Ihe lelll.'e function 4>(1'),
Ihe wooalJility of obtai/lilly/he value a. a.s a rehuit of a measurement 0/
Ihe physical qllal/lily :1 (,., II ) i8Icnl~, where c~ ih yivm by Eq. (2.'1 9)
and >fn is Ihe proper fWlc/iOlt 0/ Ihe opera/o" A(r , - ihV) corresllOllcling
10 the proper value an.
It can be shown that Eq. (2. 1) is simply a special application of this principle when
the physical quantity mcusurt.-d is jUst the position of the particle.
jOfJ The forrrw//Mory of quail/tun mMllic, /0/
Quanlum mNhallia (2.12 2.12)

According to the third I>,illclplc, when the WIl\'C function 4> is lIot 8. proper func- Since the functions are normaliud, we use I<:Q. (2.50). Therefore
tion of A, we cannot say what the exact value of A is, and if we repeatedly measure
A, we obtain many different r<!Sults, each with II. certain l>r-obability. We may,
howc\'(~r, spcsk of the a.vtrwjt or tXIH!daliOlll"Olue of A in the slate described by ....
As II. corollary of the third principle, we can show that
since the operator corn.'!;pond ing to P is - ihd/ d..L. But dt./d..L - ..t21O.(n-r;/a) COlI n-r;:r./ a.

f
Ole QL~r(1ljt or tJ:l'tdalion llOiue oj a physical quantily A Cr, p ) u"he" O,e Therefore
slale oj the Byslem corrnpolldslo IIle tUIle/ioli <I>(r) is 2n... nll"x nll".t
P ... - i A - sin-~-dx-O .
.,. a2 ..... a a
(2.50)
This may seem to contradic~ Eq. (2.13), ..... hieh stalC!! ~hat the mom~ntum of a particle
in a box isp _ nrA f a. 1I 0wever, the value p .. I'Irhlo.gl\~ the magllltudeof the momen-
To handle &t. (2.;",0), we must first operate wilh A on "', then mulliply by ... , tum. But momentum is a ,"eclor quantity and a particle m a bo~ .mov~s ?ack and forth
and finally intcgl'ate. Equation (2.1".10) is correct if the functiOIl <1> is normalized to in a symmetric way, changing the direction of illl momentum. IhlL~ It IS nalUra! that
f
olle j that is, if 4>+'" dT = I. But if <I> is not. lIormalized to one, we must write
p - O.
instead
EXAMPl.E 2.10. ",Iatriecs associated with a physical quantity.
(2.5 1)
So/uU",,; Let us consider the proper functions ~Io ~ 2, ~ 3, .... of the ha~iltonian; ~.e.,
those satisfying the equation H~ . _ I:'~ . Given that ..t is another phYSical qUlllltlty,
T he p rinciples we have staled are static in ~he sense that they give no informa- we may obtain the series of quantities
t ion about the time evolution of a system. To obtain a dynamic thCQry, lI"e 'Iced
the Jour/It l!rlllciple oj qual//um mechanics: (2.54)

I V. The lime clJO/ulion oj a physicalsyslem i8 d.scn"bed by the equation for each pair of functions"" .. snd t . Theile qlLant;lie~ can be arranged in lhe matrix form:

... iI~ H
1"iii= ~, (2.52) .112 .113 . 1\0

.122 . 123 .12

tel/ere H i8 tilt: /tamil/onia" opera/Qr oj IJ,e syslem.
.Iu .133 . 130
We see that Eq. (2.52) is identical to Eq. (2.27) in one dim ension when H is
given by &1. (2.37). Applying the idea of operators, we may say that we can ob- .1 .. 1 .1_2 . 1.3 A ....
tain the dynamical equation (2.52) by replacing the energy E in Eq. (2.38) by the
0llerntor iha/Ol .... That is, This array is called the molrix of .1; the ,I ... are the matrix clement.'!. Th: eleme~ts
. 1II, . 172, . , , .. ' are called the diagQno/ mo/ru demenl. because of the.lr
1 h
localLon
I
in the matrix. To compute the matrix of an operator, one doc~ not net:el!oSll.n y ave 0
(2.53)
use the proper fUILctions of the hamiltonian; the proper functions of any other operator
may be used instead.
We shall nol. elaborate furthe r Oil the formal theory of quantum mechanics; the The calculation of nmlr;" clemel\\.!! is vcry important in !!e"erlll ~u.antum problems.
prineipl~we have stated arc sufticient for the pUf!lOSe of this book. \\'1' shaU illustrate onl y one example. The matrix clements of the 1JQl!ltion vector are

EXAM I'tf: 2.9. Find the al'erage valuc of thc lIIomcntlU1\ of a partide in a polcntial r.. ~ - f~:rt"dT.
box, given thlLt the wal'e function eorre~ponds 10 one of IhCl stationary states.
50lloiOlO: We obtained the wave functions of Ii particle in a one-dimensional box in 1t can be proved that the transition probability from state ,i into ~t~te! with the emission
Section 2.5 a.~ or absorption of electric dipolc radiation of cnergy IH..J - I~, - 1:./ I ~ gl\'en by

.,.
",. -
~_. Jlll"X
-sm -
(2.55)

f0'2 Q!lCmlum mrnmiu 103

Thus if r,1 _ 0 , the transition is fil'l;l-ordl'r forhiddl'n. In this way we obtain the selection 2.5 Estimate the leTO-I)(Iint energy of an equal sides, find the number of quantum
rulell melltioned in Section 2.1 1. The state of polarization of the rndi!Hion ill determined electron confined inside a region of sire state!! (a) with energy be~ween E and
by the COl1l1lOnl'nt4 of r of' For example, if I,I - V,I ~ 0 but :,1 ;o! 0, the the radiation 10- 14 m, which is the order of magnitude of E + dE, (b ) with momentum between p
emitted or absorbed is polarized l)8.rallello the Z-axis. Since the I'nergy emitted. in the nuclear dimensions. Compare thill enew +
and p dp,
transi tion ill II ..., we have that the rMe of energy radi tt.tion is with both the gravitational potential energy 2.14 Verify by direct integration that
and the coulomb potential energy of an wave functions ~o and I}L for the harmonic
electron and a proton separated the lIIlme OIIcillator ('ra ble 2- 2) are normalized.
distance. On the basis of thill COmllarison, AIBo verify that 0/<0 is orthogonal to "'1
discuss the possibility that an eledron and Y,2.
,\f('r com llaring Illi" with the re~ull of EXamlJle 1.1 for 3. cla.s'!ical oscillator, we conclude can exist wilhiu a nucleus. 2.15 Calculate the zero-l)(Iint energy and
lhal durin g the transition the electron behaves M an electrical dipole of angular frequency
2.6 Calculate the tero-point energy of a the SI)8.eing for t he energy levels (a) in a
<.00 and 311 amplitude 2Ir"I.
neutron which is confined within a nucleus l-dimenBional hsrmonic oscillalor, "'ith an
which has a size 10- 15 m. OIIeillalory frequency of 400 Hz, (b) in a
2.7 Show tllat t.he fractional energy dif- three-dimCnlJional harmonic OILeillalOr with
ference tJ.E/ b' bet.ween any two adjacent an oscillatory frequ('ncy of 400 Hz, (c) in
level9 of a particle in a box is given by the CO molecule, if tJle two aloms OILcillate
1. "QU3nlum-i\lechnniCIiI Tunncling,~ J. Fenner, Am. J. Phys. 3'\, 11GB (1900) (2n+ \ )/n 2. with a frequ ency of 6.43 X lOLl Hz.
2. "The Philowphicnl Bl\.$is of Bohr'~ In terpretaHon of QUllntum Mechanics," H. Hn!!, 2.8 Normalize the wave functions for a 2.16 The gencml e.~pression of the solu-
Am. J. 1~Ii!l8 . 33, 62\ ( 19M) particle in a l)(1tential box, given by tions of SchrOdinger's equation for the
3. "Quantum i\lechllni c~ IllIIl Model," T. Buch , Am. J. Phys. 31, 653 ( 1900) Eq. (2. 18), showing tllat C - ~ - harmonic OIlcilllltor i8
4. ~ I nterprctation of Quantum ),Iechanics :lnd the Future of Physks," E. Witmer, .lm. vsrv, where V is the volume of the box.
J. Phys. 35, 40 (1967) 2.9 Prove that the three-dimen~ional wave
functions given in Eq. (2.18) are orthogonal. where N. _ ';0/r1l22n1 is the normali~
5. Klement. 0/ 1I'0~e MtC/r.OIlic" X. 1IIotl. Cambridge: C3mbridge Unil'ersity I'ress,
l!l6Z, Chnpters], 2, 3, and" 2.10 Plot the function g(p) gi\'en in Ex- tation const.ant, 0 _ vm<.oO/~, and the
ample 2.4 versus p, and COrl,1pare with functions 1f.(IU) are called Ifermil~ poly-
6. InlrodllCtitm to .Ilodvnl'hytic., F. Hichtmyer, E. Kennard, and T. Lauril$Cn. New
Fig. 2-12. Explain the difference. nomial" defined by
York: ),lcGraw-lIil1, 19as, Challter 6, Sections 96-102
2.11 Show that the \'olume of phase Bpace d" ,
7, II'kmel1Utr~ W(lt.'e ,ll tChonic., W. Heitler, second edition. Oxford: Odord l:ni\'ersily corresponding to a particle moving within If.W - (-I) ee' - (e- I ).
Press, 1956, Cha11ters I and 2 a region of volume V and having a momen- '("
8.. lIomie Spedro ond . Uom ic Slrllelurt, C. Henberg. Ne .... York : Dover Press, ]9401, tum between p and p +dp ia 4lrVp'ldp. Writ.e the first four wive functions (n - 0,
Chapter I Recalling that the minimum aiae of a cell I, 2, 3) and compare I\'jth the expressions
9. &rudure 0/ ,lIot/cr, W. Finkelnburg. New York: .-\cademie Press, ]96~, Chapler 4 in phase apace I\'ithin which a particle can given in Table 2- 2.
10. Qllontum ThtorlJ 0/ MaUte, J. Slater. i\'cw York: ),leGrnw-nill, 1951, Chapters 1,2, be localized is h3, find the number of quan. 2.17 The ,,'ave functions for a three-
and 3 , tum states with momentum between p and dimensional harmonic oscillalor can be
+
p dp accessible to the particle. Compare written as
with the results given in Example 2.4.
2.12 Show that the energy le\'els and wave >Jo.,.,.,(.t,lI,:) - N.,N.,N
fuuctions of a particle moving in the X}'- X II., (a.t:) Il., (ov) II (l~)e""""'2 ,
plane within a tll'CHiimensional potential
2.1 A Ilnrticle is repre~nlcd by lhc wal'l! 2.;1 What is the efi'l"cl on the I"nergy Je\'('I~ where the different quantities are as dc-
box of sides a and b are
function I}(x) - ~ -(._ 1'12.. sin kl. Plot of ft one-dimensioual potential box IlJI the fined in Problem 2.16. The energy of
the wal'e function I}(z) 11l1d thc Jlrobabi1it~ size of the bo~ (a) decreases? (b) increases? tile 08cillator is E - (n+ !)h<.oO, where
distribution 1o/.t)12. ]o;$li111l1le the uncer- 2.4 Consider an electron in a onc-<Iim('n- "d n _ nl + +
n2 n3. Show that the degen-
tainly in the 1)08ilion and in the momentum ~ional IlOtl"ntial bux of width 2.0 A. Cal- I} - Csin (nl1r.t/o) sin (n2lry/b). erncy of each state is g - l(n +
1}(n+ 2).
of the I)artide. culate the zerO-Jloin~ energy. Using the .'ully write out the wave functions corTe-
+
2.2 Sholl' that R T - ! for 11. stream of uncertainty principle, discuss the effcct of Discuss the degeneracy of levels when 8110nding to n _ 0, I, RIld 2. Note that
parliclea impinging on Il llOtential $te)) of
heigh~ Eo when B > Eo (rdl"r to E~
incident radiation dcoigned to locate the
electron with II 1% accuracy (that is,
a - b. Find the normalization consto.nt C,
2.13 Referring to Problem 2.12, if the
the wave function for n -
is spherically
symmetric. Analyze Ule ahallt of the wa"e
aml}le 2.2), ~.t _ 0.2 A). tWo-dimensional box is very large, but has functions for n - I.
104
,.", . K ,
2.18 What is the effect 011 the energy
levels of a one-dimcnsiolllli potentia! well
as the depth of the well (a) decreases?
(b) increases? Repeat the analysis, con-
sidering that the width changes but the
depth remains constant.
2.19 Discuss the effect 011 the energy
levels and wave functions of a potential
well of range a when a hard CQrc of range b
is added, as shown in Fig. 2- 38. [/lint:
See Examples 2.5 and 2.6.)
2.20 Given a lJ'Olential well of depth
E'o and width a (Example 2.6) draw the
possible wave functions for th e bound
states if
(a) Eoa 2 < ,..2h2/8m,
(b) ,,2h2j8m < Eoa 2 < !hr21.7/S m,
(e) !hr2/12/ 8m < Eoa 2 < 251I- 2h2/8m.
2.21 Estimate the well depth Eo for a
neutron in a one-dimensional rectangular
wcll of width 3 X lO-u m, given that its
binding energy E6 is 2.0 i\lcV, and a.s.sum-
ing that only onc energy level is possible.
2.22 Equation (2.23), k, cot k,i}. - - cr,
may be solved graphically in the following
way: Dcfine ~ _ k,a, 'I - eta, and
p - (V 2m/~'0/")a. Therefore e+
p2. Also from Eq. (2.23), 'I _ - ~ cot~.
'12 -
With ~ as abscissa and 'I as ordinate, plot
" - -~ cot ~ and show that the circle
e + ,,2 = p2 intersect~ Ule curve once,
twice, three times, etc., depending on the
value of p. The points of intersection cor-
respond to the allowed \alues of Eoa 2.
Show that these values are consistent with
the values of E0)fJ.2 given in the text.
2.23 For the square potential barrier of
Fig. 2- 23, determine the coefficients B, C,
D, and . 1' in terms of the coefficient A for
(a) E < E'o and (b) I~ > Eo.
2.24 Write the wave functions in each of
the regions of the 1lOteutial energy shown
in 1"ig. 2--39. Also sketch the wave func-
tions. Consider that the incident particles
COme from the left and discuss the three
distinct cases in which E < Eo, Eo < E <
Eo, and H > Eo.
Prob/e11U 105
2.25 Repeat the prcooding problem for a
case in which the particles are initially in-
cident from the right.
2.26 Consider the potential energy shown
in Fig. 2-40. DiscuS!! the general mat.he-
matical exprcS!!ion and the shape of the
wave function for a particle incident from
the rigM when ils energy is (a) E < Eo,
(b) Eo < E < bh, and (oj E > Eh. Re-
peat the last two cases for a particle which
is incident from the left.
2.27 Write the wave function in each of
the regions of the potential energy shown
in Fig. 2--41. Also sketch the wave func-
tions. Consider a particle incident from the
left, first with E < Eo, and then wilh
E > /<;0. Is there a lX)8Sible stationary
state for a particle initially in region (3)?
2.28 Write the wave function in cach of
the regions of the potential energy shown
in Fig. 2--42. ..\ lso sketch the wave func-
tion.
2.29 A particle moves rectilinearly under
the action of a uniform electric field 6 so
that its potential encrgy is E. - -&x.
(a) Write the Schrodinger equation for this
motion. (b) Make a sketch of the wave
functions for all energy 8 larger and smaHer
than zero. Is the energy quantized?
2.30 Gi\en the potential encrgy shown in
Fig. 2-43, sketch the wave functions for a
particle coming from the right and having
a to tal energy that is (a) negative, (b) be-
tween zero and Eo, (c) larger than Eo.
How does the wavelength of the particle
change as the particle moves in the regions
x > and x < 0, if the total energy is
larger than Eo? Repeat for a ease in which
the particle comes from the left. This
situation corres]lOnds to the potential
energy of an electron in a metal \\'hen an
e~ternal electric field 6 is apl)lied.
2.31 A particle moves under the 1lOtential
energy E.(x) - _Eoe- ,2. (a) Plot Ep(x).
Q
(b) Make a sketch of the wave functions
when the total energy is both negative and
1>ositive. (c) Do you expect to h:we quan-
tized encrgy levels for certain ranges of the
energy? (d) Estimate HIe zerO-llOint energy

106 QUlllllwn mteIlaniu
"I
I--'-+-+~I--
I---.-+
-,, --'1-
...._ (1),,[1) ~ (3)
F ig ure 2-14
of the particle. (/Jint: Note that fot ener-
gies close to - Eo the particle OfIcil!stcs
with a frequency w _ (d Zf.'JOI'd.: 2)j m1I1:l.)
2.32 Show that for the Hermite poly-
nomiab defined in Problem 2.16,
if 1\ is even and
1/.(- 0 - - II. W
if n is odd. Conclude from this !.hat the
wave functions for the one-<limcnsionsl
harmonic oscillator have even or odd
pari~y depending on whether n is c\'cn or
odd. AI.'!O show that the parity of tht:
three-dimensional harmoni c OIIcilistor of
Problem 2.17 is even (odd ) depending on
whether n is even (odd).
2.33 Show that the wa,'c functions of II.
particle in a ])()tcnlial box of Eq. (2.IS)
have even (odd) parity if n - III 112 113 + +
is odd (even) .
2.34 Given the [lO\Cnlial energy shown in
Fig. 2-44, write the wave function for each
region and sketch the wave functions and
energy levels for J:.' < 1\0 and E > Eo.
Note that the wave functions are symmet.-
ric (even) and an tiaymmetric (odd) . Dis-
cuss the elTect on adjacent energy levels as
either Eo or b becomes very large.
2.35 A particle moves with the potential
energy ~hown in Fig. 2- 45. Plot the wave
...
Figure 2-45
functions and the probability di ~tribution9
for the three lowest energy levels. Hecog-
nite that the three levels have very close
energies. l\lake a general sketch of the
energy levels.
2.36 Consider the time-dependent wave
function fnr a beam of free particlcs IL!
givcn by Eq. (2.29), where (;\12 is the
average number of particles per unit
volume. Show that the numbe r of particles
crOS!!ing a unit Ilrea per second (i.c., lhe
]Jarticle flux) is h(JI(~klm.
2.37 Given that
"'(z, I) - cl\f,. (z) e -~I " + C~';2 (z)e - ""'/I,
whcre the proper fun ctions .;. (%) and ';2(Z)
are orthogonal and normalized, show that
and .
This shows that the wave function at any
time can be found in terms of thc initial
wave function 'I'(z,O) . Extend the result
to the case in which
2.38 Show that the free-particle wp.ve
functions ';(x) _ e;h are proper func-
tions of the momentum operator corre-
SJ)()nding to the pro]lCr values "k,
resp,eetively.
2.39 Indicate which of the following fun c-
tions are proper functions of the oll'crator
dI u : (a) t 'h, (b) taL, (c) sin h. Indi cate
in each case the propcr value. RellCat for
the operntor d21lk 2
2.40 Show that the momentum operator
- iMI Ik is henoitian. I/lint: lntegrnle
the expression on thc left of F.,q. (2.40) by
]larUs, with A replaced by thc momentum
0llCrator, and take into account the be-
havior of wave functions at co.1
2.41 Find the average or expectation
values of z, %2, p, and p2 for the n .. 0 and
n .. I sta.tes of the linear harmonic
09cillator.
2.42 Find thc average or cxpcctation
va'lues of x, x 2 , p, p.nd p2 for the ground
p.nd first excited states of a particle in p.
one-<limensional I)()tcntial !xlx.
2,43 Write out fully thc OllCrators corrc-
sponding to the t1,ree rectangular COIll-
ponents of the orbital angular momentum
L _ r X p.
2.44 The commutator of two opcrators A
and 8 is A8 ~ SA and is designated by the
sym!xll [A, 81. Show that
lx, PI!.; - i/ff,
Iy, P.!.; - 0,
and
Il, p,p .. 0,
where .; is an arbitrary function. I:sually
the W!lve function is not e"plicitly written
and the relation:i are written ali [z, p.1 - ifl ,
Iy, p.1 .. 0, and [z, p.1 .. O. (Commuta-
tors playa very import.a.nt role in quantum
mechanics. )
2.45 Find the matrix clementl! XOIo :1:02,
POI, and po~ fOf the coordinates and
107
momenta of a lincsr (o nc.dimensionsl)
harmonic oscillator.
2A6 A IlJlrt icle move:i in a one-dimen-
sionsl ])()tential box of width a. From the
normalized wave functi ons find the matrix
clemen \!! z ... aud p.... Show also that
p . .. .. imw...z . .. , where
w. .. - (fl . - E.. )/ h.
2.4i Find the selection rule for the elec-
tri c dij)()\e transition of a particle in a one-
dimensional l)()tenlip.1 box. IHinl: Recall
Exam]llc 2.10.]
2.48 Show that if 0/1. and 0/12 are indepen-
dent pTOllC r (ullctions of a linear operator
corrCl!ponding 10 the same degenerate
proper value, the function 4> - e.';1 + (21/12
is also a Ilroper function of the operll.tor
corres])()nding to the same degenerate
prO]lCf \nlue. Show al~o that if 0/11 and 0/12
are not orthogonal it is possible, hy a choice
of constants, to lIlake the proper function
<I> normalized and orthogonal to 0/1 . Thi5
l"C!lul~ is imp-ortan~ because it sho"'~ that
the proper fun etions corl"C:!S])()n(\ing to
degenerate proper \ ' '''\UCll can always be
assumed to be orthogonal. Ext.end the
method to the case of three proper func-
lions ';1 , ';2, ';3, by making two linear
combinations <1>1 and <1>2 of the;jC three
functions tha t are norlllp.lixed and orthog-
ollal to >/I .
2.49 The eun'ature of a function .,(z) is
prol)()rtional to ~/u2 . l'sing Schrodin-
ger'a equation, !!how that if E < E.(z) ,
th e wave fun ction ';(z) is concave toward
the X-asi~ , p.nd that if g > I~'.(z), the
WIL\'C function '; (z) is eonve.~ toward the
X-axis. Check this result with the ploUi
of wave fun ctions considered in this
chp.pter.

3
ATOMS WITH ONE
ELECTRON
3.1 I nlrodllclion
3.2 Th e /-Iydrogerl Atom
3.3 Th e Specfrwn oj J-Iydrogen
3.4 Quantization of An{Jular Momentum
3.5 One-Electron Wave Functions Under Ceniral Forces
3.6 The Zeeman Effect
3.7 Electron Spin
3.8 Addition of Angular l\'tomenia
3.9 Spin-Orbillnleraclion
3.2) TM hydrogen olom 109
:1.1 IntnHluction
We shall begin our study of atoms by sUmmarizing our fundamental ideas about.
atomic structure. Every atom has an overall dimension of about 10-' m. It is
composed of a relatively massive nucleus (whose dimensions arc of the order of
10-) 4 Ill) about which move a number of electrons, each of cha rge - e, OCCUI)ying the
rest. of the atomic volume. The nucleus is composed of A ])articles (A is the mass
numbtr) called nucleons, of which Z arc protons (Z is the tUQmic number), each of
charge +e, and N (= A - Z) arc neutrons, which have no electric charge. There-
fore the nucleus possesses a pooitive charge of + Ze. The number of clectrons ill any
atom is equal to the number of protons (that. is, Z of them) and therefore an atOm
is an electrically neutral system. However, in eertain instances an atom may gain
or 1()S(lllOme electrons, so that it becomes negatively or positively charged; in this
case it is called all ion. The mass of the nueloon is about 1850 timO!J the electron
mass. Thus the mass of an atom is Ilraetically equal to that of its nucleus.
However, the Z electrons of an atom are responsible for most of the atomic
properties which are reflccted in the properties of matter in bulk, 8uch as the
clastic and electromagnetic prollCrties of different materials. Electromagnetic
interactions between electrons and nuclei of diffcrent atoms play the basic role in
the binding together of atoms to fonn molecules, in chemical reactions, and in
practically all the properties of matter in bulk.
We can explain the motion of the elcctrons around the nuc.leW! if we consider
only the electromagnetic interactions between the electrons and the components
of the nucleus (protons and neutrons). Since electromagnetic interactions are well
understood , it has been possible to develop an accurate description of the electronic
motion. The corresponding problem fo r the nucleus, on the other hand, is more
complex, since other interactions entcr which are not so well undcrstood. When we
analyze clectronic motion, we must use the methods of quantum mechanics dis-
cussed in the previous chapter.
In this chapter we shall discuss the properties of atoms and ions having just one
electron (of which the simplest is the hydrogen atom) and in the following chapter
we shall consider the problem of many-electron atoms. Thc onc-clectron atom will
hclp us to understand the basic problems related to atomic stmctuN!.
3.2 The lIydroge,. Alom
The simplest of all atoms is the hydrogen atom. Its nucleus is composed of only one
particle, a proton, so that it h8l:l A = I and Z = I. Around the proton, a single
electron moves. So that our cn.lcu!ation will be applicable to other atoms we shaH
assumc, however, that the nucleus contains Z prolons with a total positive charge
equal to + Ze (Fig. 3-1). At this moment. we shall make two approximations. First,
we shall consider the nucleus to be at rcst in an inertial system. This is a reasonable
assumption because the nucleus, being more massive than the electron, practically
coincides with the center ofmlWJ of the atom, which certainly is at rest ill an inertial
SYlJtem so long 8l:I no externAl forces act on the atom. Second, we shall assume that
the electric field of the nucleus is that of a point charge. This is also reasonable,

110 (3.2 3.2)

since the nucleus has a very small size (about 10- 14 m), compared with the average T he possible energy levels for the 9t&-
distance of the electron from the nucleus (about IO-I() m). However, in a more tionnry bound states of the electron,
refined analysis, the size and shape of the nucleus would have to be taken into which we obtain from Eq. (3.3), are
account. given by the expression

13.6 cY I --- 2 --- 3

2.180 X 1O- 18Z 2 20

F J, (3.5)
Fig. 3-1. An elect ron moving around a nuc!eUII. n'
where 71 = I, 2, 3, (IX'Sitive inte-
30 ---2
gers). Sometimes it is more convenient
to express the resul t in electron volts.
~I:lking the proper changCl! in the
units, we get ,V
. .-

E "'" ~ 13.GOi Z
The motion of the electron relative to the nucleus is determined by the coulomb 2
V (3.6)
interaction bdwccn the two. This interaction is expressed by an attractive inverse- " ,f z e. 50
square central force act.ing on the electron, given by
:\'ote that the values of the totnl energy
are negative. This is in agr'C(!ment. with
(3. 1)
the classical resul t. for motion under an '" .,
inverse-S<IU!l.re foree when the orbit is ~
The potential energy of the electron-nucleus system is then ellipti cnl or bound. The zero point of

E,(r) = - - - .
z,'
41rE ol'"
(3.2)
the energy is assigned to the state in
which the two p!l.rticles (electron and "t
I~Jr
nucleus) arc at rest nt an infinite dis-
H owever, since we must anaJyze the molion of the electron by means of quantum tance ap,'lrt. T herefore, Eq. (3.6) is
In.SeY I
mechanics, we cannot solve the problem by applying the Newtonian equation of equimlent to the energy, in classical
motion F = dp jdJ,; instead we must set up ~hrOOingerJs equation for motion, mechanics, fo r the mo tion of I>arlicles in
with a potential energy given hy Eq. (3.2). Because the electronic motion is th ree- ellipticnl orbits; however, let us remind F ig. 3-2. Somc energy Icvels of 11 , He+,
dimensional, we must use Eq. (2.9). This results in a SchrOdinger equation of the the reader that one does not talk about and Li'+.
(0= precise orbit1'l in quantum mechanics.
Expression (3.6) applies to any atom which has a single electron. T hus it holds
(3.3) for hydrogen (Z = I) and its isotol>CS, deutcrium (A = 2, Z = 1) and tritiwll
(A = 3, Z "" I); for singly ionized helium, Hc+ (a helium atom that has lost olle
The solution of this equation is an aniuous mathematical problem, for which the of its two electrons, Z = 2); for doubly ionized lithium LiH (a lithium atom that
student is not yet properly equipped. For the present, we shall limit ourselves to a has lost two of its three electrons, Z = 3), etc. r'igure 3-2 shows the CQrrcsponding
consideration of the energy of the stationary states. We shall discuss the wave theoretical cnergy levels. 'I'he approlHiatc values of 11 are indicated for some levels
func tions y, in Section 3.4. in each series.
Let us introduce a constan t, called Rydberg'a constant, defined by Note that some levcls in Fig. 3-2 arc coincident. Por examplc, hydrogen levels
coincide respectively wilh the I cvcl~ of He+ which have 11 = 2, 4,6, . .. and also
m..-' = 1.0974 X 107 m- I with those of l.i 2 +, which have n = 3, 6, 9, . .. The reason for this is that some
R. = - . (3.4)
8f~3c COmmon factors lIrc canceled in Eq. (3.6) due to the respective values of Z. The
coincidencc, howcver, docs not occur cxaetly in nature. The nuclcus is not at rest
The rell!On for the ~ub8crip t 00 will be apparent latcr on. ill an inertial frame; rather the Ilucleus and the electron rotate about their center
 3.2) The hydrOiftn ulom 113
112 Afonu with Oll~ tI~c/rcm (3.'

TAIILE 3-1 ll ydbcfg"8 Cons ta n t

(R., _ 10,973,131 m - I )

, ,, ,,
,,,
Atom Z A R,m
, ,,
Hydrogen (II) I I 10,967 ,758
Deuterium (D) I 2 10,970,742
Fig. 3-3. Standing wavClS on a circle.
Tritium ('1') I 3 10,971,735
Helium (lIe+)
Lithium (Uz +)
2
3

7
10,972,227
10,972,880
,, ,
Beryllium (UeH )
9 10,973,070 ,, , ,/
of ml1S8. However, we can nnlliyze the relative motion of the electron and the
nucleus by substituting, in Eq. (3.4), the reduced mass of the electron-nucleus
system for the electron mass. Gi ven that. /II is the mass of the nucleus, then the
reduced nlMS of the atom is it seems logical that it must be able to sustain standing wllves of wllveleng\h ),. - hl p.
We can see from Fig. 3-3 that thi~ requires that the length of the orbit be equal to an
integral multiple of iI.; that is, 21fr - nil. - nh / p or
rp _ nhI 21T. (3.S)
T herefore in Eq. (3.5) we must rcplnce Rydberg's constall~ R .. by
Noting that rp is the angulllr momentum of the electron, we !ICC that the stationary statcs
n =~= R .. .E... ::!'n.. ( I + mI ~/M) , (3.7) are those for which the angular momentum is an integral mUltiple of I, - hl 2r. 8mce
8t~3c me p _ 111011, we may also write Eq. (3.8) as
(3.9)
SO that the energy levels flrc given by E = - RhcZ'l/n~. The value of R for scv- m",:r - nh/ 2r
erailluclci is given in Table 3- 1. Obviously R", corresponds to the C3.SC in which On the other hand, the equation of motion for the electron requires that P - m0ll2/ r,
the nucleus 11M infinite m9S8 (M = 00), and this explains the reason for the sub- where P ig the centripetal force. But in thc case of an electron moving about a nucleus,
script on the symbol. the eentripetal foree is the coulomb force given by Eq. (3. 1) . Therefore
So far we have considered only slales of negative energy, or bound ,(aie,. The
state<! of I>ositive energy, which in a classical description correspond to hyperbolic (3.10)
orbits, are ulloowul ,tate" in which all electron with enough kinetic encrgy
approaches the nucleus from a great distance and, after being deviated from its When we eliminate u between Eqs. (3.9) and (3.10), we have
straight-line Illotion by its coulomb interaction with the nucleus, recedes again
toward infinity. As eXI)lained in Section 2.7, positive energy stales arc not quan n2h210 ..2
(3.11)
tized, since the initial kinetic cnergy may have any arbitrary value and thus thcy r - ~m.:ze2 - Z (10,
form a continuum of states. where
,
(10 ~ h t 0 _ 5.2917 X 10- 11 m (3.12)
EXAMI' I.E 3. 1. Semiclll.8l!.ica! derivation of the expression for the energy levels of .m~
2
hydrogen.
is called the Bohr rodill&. Expression (3. 1 I) givcs the radii of the allowed circular orbits
So/urion: We may justify Eq. (3.5) for lhe sta liOMry slates of the hyd rogenlike atom8 and the Dohr radius, (10, is thc "radius" of the ground-state orbit (n - \ ) in hyd rogen
just as, at the end of Section 2.5, we justified the energy levels for a particle moving in a (Z _ 1).
potential box by using concepts derived from our knowledge of standing waves. Let U8 When we use Eq . (3.2) for lhc potential energy of the electron- nucleus system, wc may
8UPlJOse that the electron de~ribe8 a circular orbit, as shown in Fig. 3-3. Its momentum p express the energy of the electron in a circular orbit as:
is constant for a circular orbit. In order that the orbit corrcslJOnd to a ~tation!lry stalC,

Sec, for examl)le, Fl4nd(lmenl(l/ UnitV'&ily Physic&, Volume I, Section 9.-3.

 ..
114 Atoou with olZe eltttrOl! (3.2 3.3) The ,pulrum of hydrogm II'

Hence, if we use Eq. (3.10) to rliminate 1I!J)'l, we obtain TARLE 3- 2 .:n ergy Cor rec tio ns When Nuclca r Motion b
Con@idered
(3.13)
D 'I' Ile+ Li 2 +
Introducing lhe value of T Il3 given by l:AI. (3.11 ), we hll,'c
Atom
.1
" 2 3 7

E_ R..h<Z'
-- -- , (mol.lf) X 104 5.45 2.i5 1.8:.l 1.36 O.iS

" - (c.f.'I K), % 0.0545 0.0275 0.0 182 0.0136 O.OOiS

which agrees with Eqs. (3.4) and (3.6). lIowever, a word of Cllution concerning our
derivation: Besides being applicable only to ci rcular orbits, it all depends on the validity
of Eq. (3.8), whieh we ~hflll diSCn!!!! in more detaillatcr (Section 3.4) . On lhe other hand, 3.:1 The Spectrum fll "ydrog~n
the concept of orbit must be considered here as applying to the region in which the electron
is mo~t likely to be found, and &t. (3. 11) is only an indication of the magnitude of the As we saw in Fig. 3-2, the energy of lhe stationary slates incrca.scs with the quan+
region in which the clCClrOIl moves most of the lime, and thus of the size of the atom. tum number 11. The differcnee in energy between th e levels corresponding to 111
Combining Eq~. (3. 9) and (3.11), we find thai lIle velocity of the electron in 11 stationary and 112 (with liZ > nd for a hydrogenlikc ion is
orbit i~

We must consider this result as indicating only the order of mflgnitude of the vclocity When we apply Bohr's condition, ,, =
(E 2 - 1':1) / 11 (<1. 1.29), and neglect recoil
of the electron. Note that the velocity decreases when the energy increll.SCS (larger value effects, the frc<luency of the elcctromagnetie radiation emilled or abso rbed by the
of n). Also we have that vIc _ 7 X 10 - 3 Zl n, and thus ~ c, except for lllrgc values of Z atom ill a tmnsition between states corresponding to 1!1 and 71: is
and small values of n. lienee relativistic corrections are not very important except when
great accuracy is desired. lIowe\"('r, these corrections fire "cry im]lortant from the
thooretical ]loint of view.

EX"IMPU; J .2. Estimate lhe magnitude of the correction term in Eq. (3.7), due to the
nu clear motion, for the energy of the stationary states of the light('!lt atoms; that is, (3.14)
H, D , T , He+, and 1.;2+.
Solution : Since m./M is a I'ery lImall quantity, we may, by ll$ing the allllro.~ imation
(I + z)-I _ I - z + ... ,
"'rite Eq. (3.7) ll3 Spectroscopists sometimes prefer to usc the lC(lt~ 1IIm!~r V = "/c = 1/ >.. rather
than the frequency." Their reasoning is that spectroscopiC measurements usually
R - _. (1 - .....II ) detennine wavelength and not frequeney . T he wave number in the i\ U{SC system
is given in m- I , although the most common unit ii! em - I. In thi.s ease the above
The IIlll8!l of an atom of mIlS!! number .1 can be written, to a good approximation, as equation becomes
M - 1.67 X 10- 27 11 kg and III. _ 9.11 X IO - al kg. Thus m./.l1 _ 5.45 X 10- 4 / ..1.
Therefore !!ince thc energy is Ilrop-ortional to R, we may write v- -
RZ2 (-.!.. _ -.!..) =
1l
11!
2'
n2
10974 X 10$ Z2 (..l _..!. )
2
"It!
2
n2
em-!
llE __ !!! __ 100 me% _ _ 5045 X 10-2 %
E M M A' T his expression (or the preceding one) is called Balmer's/ormula, and is applicable
where llE is thQ ellll.nge in Qncr!!;y from the value givcn in Eq. (3.S). ThQ results for the only to hydrogenlike atoms. Since in a spectroscope (either prism or gmting), caeh
lightest elements flrc indicated in Table 3-2. "- transition appears as a line (which is the image of the slit), the spcctrum is ealk.J a
The fact Ihatc.I~/ I~' illdiffcrent for 1[, D, and T means that the energy levels for these tiue spec/rum, and fre<luently the words line and tmnsition arc used M synonyms.
three hydrogen isotopcH are slightly displaced, resulting in what i.~ c!Iolled fin iMJIopic tJJccl.
Similarly, the e,'cn levels of lIe + do not exactly coincide with tJlose of II. h was this .. The wavc Ilumber; gives the number of wavelength!! in one unit of length, and it should
minor different-c that led to the discovery of helium by Fn:mkland 1lnd Lockycr when they not be confused wi th the wave number k _ 2-,:/A, which is associated with a rmrticlc, lind
analyl"oCd the solar spectrum in IS68. which was defined in Sectioll 1.10.

118 Atoms with on~ tltclron (3.4 3.4) QU(UI/izalion of angular ~nlwn

TABLE 3-3 De8ig na lio n of Ang u la r Mome nt u m States and z z

Euenlill l Ikge n e rll cy for Motion Und e r Cen tral
Fore"
----...........,
Angular momentum, I 0 1 2 3 4 5 ",,_+2 --------
, ,
Symbol

~+ '
p d g h
--- ........
,,
Degeneracy, (I - 1 3 5 7 9
" ,,
",,-+1 ---
\,
,,
angular momentum is quantized; i.e., it may have only discrete values. It. can be
,
, I
"'1_0 ,
,,,
shown (see Example 3.4) that the magnitude of the angular momentum is charac-
te rized by the values ,,,
, m, __ 1 --- ,
,,
(3. 15) NI! _ - \

where 1 = 0, 1,2,3, ... is a positive integer. However, in hydrogcnlikc atoms the

---"/ ,,
values of I for each energy level arc limited by the values of n corresponding to the
NII_ - 2
/
--------
energy level, and the maximum value of I is n - 1. Therefore
in a coulomb field, for each value oj n, specifying an energy level, there ,/
are ,~ distillCt values of Ihe allgular momentum from l = 0 to l = n - I.
/_ 1 1-2
It is customary to designate the possible values of I by means of letters, according (,,) (Ii)
to the scheme of Table 3-3. Therefore for Il = I we have I = 0 or Si for 11. = 2 we
Fig. 3-6. Space quantization illustrated (or I _ 1 &rld j - 2.
have l = 0 and I or sand p. I'-or n = 3, it is l = 0, 1, and 2 or s, p, and d, etc.
In a central field different from the coulomb field the values of l as:wciated with
each encrgy level are also different. For example, in the case of a three-dimellsional for each value of the angular nwmenlum , IMre art. 21 + I values of ffl,
oscillator the I>otentiai energy is E, = !kr 1 The possible energy levels are r; = or 21 + I different orienlalioIU of I.
(n +t)hw (sec Eq. 2.22), and for each n the I values are n, n - 2, n - 4, ... ,
I or O. Thcn for n = 0 we have I = 0 or 8; for 11. = I, I = I or Pi for n = 2, Figure 3- 6 illustrates this situation fo r l = I and I = 2. T he quantity 9 = 21+ 1
l = 0 and 20r sand d, and soon. is called the ellllt.ntial rkgene.racy of the angula r momentum state. I t can be proved
In addition t() its limitation with regard t() its that this degeneracy is a consequence of the spherical symmetry of the motion
magnitude, experimental evidence (to be discussed z under a central force. The values of 9 for a few angular momentum values are given
in T able 3-3.

------~--- -,
later) indicates that the angular momentum is re-
stricted in direction , a si tuation called space quan- In classical mechanics the angular momentum under a central force is constant
tumion. This means that the angle L makes with the ,, , in magnitude and direction. However, in qua ntum mechanics. the magnitude of
the angular momentum is given by Eq. (3.15) and of one of its components by
Z-axis (Fig. 3-5) is not fLrbitrarY i ill other words, it
can be shown (see Example 3.4) that the values of the
component 1... arc quantized and given by
" I
" -
-- __ I

---------"' I.
(3. t 6)
where Ill! = 0, I, 2, 3, ... , I; that is, 111, is a
positive or ncgativc integer from 0 to t. The quantum
number Ill, cannot be larger than l because L, would
then be larger than ILl, whieh is impossible. Therefore
we conclude that :
Eq. (3. 16). B u~ to specify the direction of the angular momentum, we need to
know the two other components, L~ and L~. A detailed analysis, which will not
be reproduced here because of its mathematical complexity, shows that
it is impossible to know, exactly, more tlian one componellt of the angular
momentum.
o Therefore, if we know L" our knowledge of L~ and LII is at best within the un-
I'
certainties AL~ and aLII, which satisfy the uncertainty relation
x Fig ure 3-5 aL z 61..11 ;? !hL .

120 AlolIU with Ofl~ tlte/roo (3.4
3.5) Ont-diroll IOOtte fundiorn Wldu u nItal foru, 12/

This relation is similar to the uncertainty relations for position and momentum
T hese selection rules are imposed by the law of consefvati on of angular momentum,
(Eq. 1.48), and for energy and time (Eq. 1.49). In other words,
since the emitted Of absorbed photon carries angular momentum; thcrefore the
in quantum mechaniu. it i~ im~ole to precisely determine Ihe angular momcntwn of the atom must change to compcnsate fOf the angular
direction oj the angular momentum. momcntwn carried by the emitted or absorbed photon, The law of conscrvatiOll
of angular momentum and the quantum rule for addition of angular momenta (sec
Since we can know only ILl and L., we may picture the angular momentum vector Section 3.8) would allow.lll = 0, 1. However, the parity of the wave functions
L in Fig. 3-5 as precessing around the Z-axis, at a constant angle 6. in a central potential (to be discussed ill Section 3.5) forbids the possibility that
From this discussioll we may conclude .Ill = O.

>0/ '8 /-,

that the energy levels of hydrogcnlike 1_2 /_3
The selection rules (3. 17) require that transitions occur only between angular
/- 0
atoms are somewhat more complex than momentUIll states in adjacent columns of Fig. 3-7. Some of these possible transitions
the simple picture implied in Eq. (3.6) have been indicated. Note that, according to these rules, the state 2s cannot change
and fig. 3-2. In a coulomb fie ld each 7 - - into state Is, which is the only lower-lying level available. For that. reason the state
energy level, corresponding to a given n, Zs is called a mt la.s/able slale. The rules (3. 17) arc valid for elcctric-dipolc transi-
6--
contains 11 different angular momentum lions, which arc the most probable. For other tmnsitions, sueh as magnctic-dipole
states, all with the same energy and with 51 or electric-quadrupole trnnsitions, the selection rulcs nrc difTerent; these transitiolls
l ronging from zero to 11 - 1 (this is have a much lower probability than electric-dipole transitions. For this reason, ill
shown in Fig. 3-7). T hese levels are in- atomic spectra, usually only electric-dipole transi tions are taken into account.
dicated by f! B, TIp, 11d, etc. (T his result 4 Let us now comment on Eq. (3.8). Noting that for a circular orbit rp is the
agrees with the classical description of angular momentum L, we sec that Eq. (3.8) reads L = /Jh. But this rcsult dis-
motion under an inverse-square force, for agrees with EiJ. (3.15), which is L = ";/(/ + I)A. H ence the simple and intuitive
which the energy is independent of the model used in Example 3.1 for obtaining Eq. (3.8) is incorrect (although the result
a.ngular momentum, although the eccen- obtained is correct). This again warns the student that it is not possible, unless one
tricity of the elli ptical orbi ts depends on takes great ca.re, to extrapolate wave concept.8 whcn they are apillied to quantum
the angular momentum.) In a more re-
fined theory of one-clectron atoms which
, mechanics. I n this case of angular momentum, the discrepancy is due to the fact
that it is impossible to confine the electron waves to a strict cireular path. However,
takes into account other effects (such as " '" setting l = It - I in Eq. (3. 15), we get
relativistic corrections), the different an-
gular momentum states corresponding to L2 = (II - 1)'IA 2 = (n 2 _ t1)h2.
the same 11 appear with different energies.
If 11 is large we may approximate this expression by writing L2 = ,,2h 2 or L = nh
which agrees with Eq. (3.8). Thus l = /I - 1 with II large approximates til;
Fig. 3-7. Tran!itions among different an-
gular momentum Slates. 13 el~ical circular orbits. This is an illustration of Bohr's corwlpollderu:e Wincipie,
whIch states that for large quantum numbers the (IUantum description approaches
the classical deseription.
If the force is not inverse-square, those levels whieh have the same value of II but
different angular momenta (i.e., levels liS, np, 1Id, etc.) do not necessarily all have :1.5 One -I::lf'c( ron U 'a,f "unrtlonlf I : ndf'r f; vnlral Forces
the same energy. Thus under central forces, the energy depends in general on II
and l, but it cannot del>cnd on ml, since in a central field of force the orientation of T hn wave function Hx, y, z) for hydrogcnlike atoms ill obtained by solving
the orbit is irrelevant. SchrOdinger's equation, Eq. (3.3). The potential energy which appears in that
T he fact that each level in a hydrogenlikc atom is composed of severnl angular equation, E" = -Ze~/47rfor, corresponds to a eentrnl foree. We may expect that
momentum states is, however, important from the point of view of the transitions. t~lC wave funct ions of alt central-force problems [i.e., problems in which the poten-
For motion in a centrnl-force potential, the selection rules for electric-dipole transi- llal energy is only a function of the distance and therefore has the form H,,{r)J have
tions are a certain similarity.
. Because of the spherical symmetry of the I>otentiai cnergy, we can simplify the
al "", I, amI = 0, I. (3. 17) dlscUSljion of ecntrnl-foree problems by using the SI)herical coordinates r, 9, <t>

..

(3.5 3.5) 123

TABLE 34 Angu lur FUnCl ion$ Co rre3,.onding

to L2 ulld I.,

m, Angular function
,,P(.t, ~,:)
o 0 l'oo - I / ~
,

. ",
,:: - ,cos~
l
0 l' '0 - Y;!/ 4K cos 9
}' I I - =FY3/ 8l1" sill 6 e*"

- 'sine ,!~, I' 0 }'20 - ;Y5/ 4T (3 eos 2 8 - I)

~-~---- / 2 l 1'2:1: 1 - =F-..I15/ S.. siIl6 eos 6 e*"
X
2 r 2.:l:2 -' ! -..I 15/ 2K 8ill 2 6 r'2<o
Fig, 3-8. Spherical coordinates. Fig. 3-9. AngulAr wave fUllction for
8-states (I - 0).

TABLE 3-J ,\n g ul ar F " lI c lions Co rres lKlnding

(Fig. 3- 8). We can show that the wnve function for a single electron in !I. ecntral 10 1. 2 lind I.f
field can be written as a product of two factors, one that depends on the dist.ance
/ Im,1
.-
of the electron from the origin and another that depends on the orientatioll of the Allgular function
position vector T , given by the nngles 9 and 1/>. Thus we may writc the wave
fWlction as 0 0 1/ V4r"
0 I). - y3/4T cos 9
~(r, 9, 1/ = R(r) 1'(6, 1/.

The radial part R(r) depends on the l>articular (onn of the potential cncrgy Ep(r)
corresponding to the force acting on the electron. However, since the angular part
Y(6, 1/ is a consequence of the spherical symmetry of the central force, it is inde-
pendent of the particular fo rm of the potcntial energy Ep{r). In other words, the
angular junctions y(6, 1/ are the same for all celltral-force problems.
We lShall not analyze how to obtain the wave functions, although it is a straight-
forward mathematical problcm (sec Example 3.4). Instead we shall discuss the
most important properties of the wave functions.
I I~ a Mztral-force problem the angular part of the u'at't! function is
tktermined entirely by the magnitude and the Z-compo'zent of the angular
momentum of the electron.
The magnitude of the angular momcntum is detennined by the quan tum number l
and the Z-component or oricntation is detcnnined by lIZ ,. For that TCa.<;(I1i the
angular functions corresponding to $pecific values of 1,,2 and L. will be designated
as y, ... (6, 1/. Mathcmaticians call these functions spherical harmQl!i~s ..
Table 3-4 gives the angular functions Y, ... for l = 0, 1, and 2. Th,s IS the form
which is o,l>plica.ble to most physical problems. Table 3-5 gives the angular func-
tions in a form more suitable to the discussion of molecular binding. The functions
in Table 3-5 do not belong to a particular value of mz, but. of IIIr
or Im,Land they
correspond to L2 and L: instead of L .
p. - -..1 3/ 4.. sin 6 cos I/>
P. - -..13/ 4.. sin 9 sin I/>
0 d 3.1_.1 - -..15/ 1611" (3 oos2 9 - I)
2 d.. - -..115/ 4"11" sin 9 cos 9 co~ I/>
d M - y15/ 411" sin (j CQS 9 sin I/>
2
d,' _' - ~ sin 2 (J coo 24>
d., - v'i574i 8i n 2 6 sin 24>
From Table 3-5 we can see that for l "'" 0 (or s-states), the only wave function is
independent of the angles; that is, s-liaus are spherically 8ymnutric. We can see
this in the polar diagram of Fig. 3- 9, where the value of the s-function for each
direetion (6, 1/ is indicated by the length of a line from the origin. The locus of the
end points results in a spherical surface. This result is understandable because, if
the angular momcntum is zero, there is no prcferred orientation of the electron's
orbit.
For l = I (or I>-states), thcrc a re three angular functions, representing the three
POSsible orientations of the angular momentum or the three values of nil = 0, I.
Table 3-5 Jesignates them as PJr, Pw, and P. and they are shown in the polar dia-
gram8 or Fig. 3-10. These functions correspond to a preferred motion of the

AfOITII with on~ dfNI
{3.5 3.5) On~dI"on lOON /uru;liom ulldu etl/lrol/orU6 1 ~5

z z z TAB LE 3-6 Ra di a l Wave Func t ion 8 of Hydrogen li ke

Ato m s

R {r) (p _ 2Zr/ noo)

"
I' o
y y
,
x o
., x 2
Fig. 3-10. Augular wave functioIUI for p-states (I - I).

o R30(r) -
1 (Z) 3/2 (0 -
. p; - 6p + p2)e_'/~
!:Iv 3 00

3 R3J(r) - - -
1 (Z)
-
3/2 p(4 - p)e
_./ ~
9\1"6 00

f
2

x An important property of the angular functions Y I . , is that they have a parity

d._
z and are odd functions. It can be shown that for electric-di]>ole transitions the initial
Fig. 3-11 . Allgular wave funct ions for d-states (I - 2).
electron a.long each of the coordinate axes, a result that is very important for
describing chemical binding. - .
For l '=' 2 (or d-statcs), there are five different angular fWletLons. The .angular
distribution of these stat.ca is more complex, as we can see from the polar <iLagrams
of Fig. 3-11, which represent the d-functions of Table 3-5. For larger valuC:!l of I,
the situation becomes even more complCJr.
equal to (- 1)1. That is, for I = 0, 2, 4, ... , even integer, the functions )', ... have
the same value and sign at points symmetrically situated relative to the origin of
coordinates, and thus are even functions, while for 1 '"'" 1,3,5, ... , odd integer,
the functions J',_, have the same value but opposite signs at symmetric points,
and final Slates must have opposite parities, and therefore these states call1lot have
the same value of I. For that reason the value III "" 0 is impossible fo r these
transitions, as previously indicated in connection with Eq. (3. 17).
The radial part R (r) of the wave fUllction y,(r, 8, ~) depends on the energy and
the magnitude of t he angular momentum, but not on its orientntion. We can under-
stand this bceausc the spherical symmetry of a central field indicates Lhat the radial
distribution of the electron's motion must be independent of the orientation of its
angular momentum; that is, it must be independent of the value of nil. This is the
quantum analog of the classical result that the energy and the magnitude of the
angular momentum determine the ~size" of the orbit. Therefore the radial function
dC]:Hmds on the quantum number 1/ associated with the energy, and on I, but 110t on
mI. Thus these radial functions are written as U~t<r) , and the total wave functions
become
(3. 18)
Table 3-6 gives the radial functions corresponding to the first three energy levels
of hydrogenlike atoms. These fUllctionsare shown ill Fig. 3- 12. The dashed line in
each C8;je indicates the classical radius of the orbit, in accordance with Eq. (3. 11 ).
 ..
,2< (H 3.5) Oll~ltdron toot't/ulII;{ioru undu ctn/r(lI/0I'6 127

We can see that, although the electron is mos~ likely to be found within the
Z.O 1.0 classical rnd ius of the orbit, it may also be found at larger distances. The probabi!it.y
of finding the electron within 0. spherical shell of radii rand r +
dr, regardless of its
, /- 0
angular position, is proportional to r l [R .. 1(r)]2 (see Problem 3.25). Figure 3--13
shows thC:!lC probabilities.
' .0 0.' One interesting peculiarity, easily appreciated by looking at Fig. 3-12, is that the
radial fWletions for &-electrons are relatively large (or small r. We say that the
&-electrons describe penetrating orbits reaching very close to the nucleus. T he
/- 0 p-clectr6ns are less penetrating, the d-electrons even less so, and so on for higher
values of the angular momentum. T his is caay to undersrnnd if we consider that
(in both classical and qu.o.ntum mechallics) the radial motion under a central force
O
.4 b;:, O.2~ 1.. \ corresponds to an effective potential

0, 8 o .
u:
,
O~ '
12
E. .ofr = E.(r)
L'l
+ 2-----;
mr =

E.(r) + l(l 2+mr1)h
'
2
(3.19)
r, A O. I~
where E.(r) is the potential energy of the central force (the coulomb potential in the
o ~ria 8
12
r, A case of an electron) a nd 2 /2mr~ is called the cenlrlfugal 'fWlential (sec Example 3.5).
For s-states we have I = 0 and there is no centrifugal potential, so that E .err =
Fig. 3-12. Radial wave functions of hydrogen for n - I, 2, and 3. The ordinate of the E. Thus a bound s-electron with negative energy E (Fig. 3-14a) can classically
curves in each case ill IN.I(') m- 312] X 10- 8. move between 0 and A, and therefore has access to the origin of coonlinates. The
shape of ~he radial part of the wave fWlction must then he as shown at the bottom
of the figure. (T he number of oscillations of the wave function depends on the
energy.) But for other values of the angular momentum, the shape of the effective
potenl.ial is as shown in Fig. 3- l4(b). Therefore nn clectron of energy B must move

1
classically between Band C. We translate this into quantum-mechanieallanguage

w~
by stating that the wave function must decrease very rnpidly outside the classical
limits of motion, and must therefore be very small near the origin. The larger the
angular momentum, the further the wave function is pushed away from the origin
'00 and the less ~pcnetrnting " is the orbit.
o .. ! 8 12
T his eharnctcristic of electron motion is reflected in many important properties
80 of the atom. For example, s-electrons arc very sensitive to the shape and internal

OJ

..
/- 0
00
wlA
o .. S 12
structure of the nucleus, while electrons with largcr angular momen tum are much
less sensitive to nuclear shape and structure.

EX AMPLE 3..1. Anal y~i~ o( angular momentum operators and proper (unctions .
Solu rio,. , We recall from Table 2--4, Section 2.12, that the angular momcntum operator
is given by
2<l

L - -ihr x V - -ih
".x ".II ".' I,
, IJ/ ilx J/ ay a/a:
0 ;

"
2
.
r, .\
I;

from which we concludc tha t the Z-componcn t i~

Fig. 3-1 3. Radial probabitit; dilllribution in hydrogen for n - 1, 2, and 3. The ordinate
in each C&Se i~ [r 2 R.,(r) m- I ] X 10- 16
L. _ _ lh
. ('
X - - lI -
ay ')
ax
, (3.20)
 ..
(3.5 3.5) Ol!e~leclrol! ware Jundiol!$ UJUkr cenlral JorU$ 129
A /oms with on~ ~ltclron

E E ,, and the operator l . can be written in the form'

\ Centrifugal ]X>tentiaH(l+ 1)/,-2 l _ -ihg, . (3.21)

,, , '0
,, H can be shown thR;t thi s rela tion is absolutely general aud that the quantum operator
" corresponding to the component of the angular momentum along any direction is given by
__________-4A~___ '-- - if, al a"" where q, is an angle measured around the direction. The proper equation,
O~~---4c' -
O~
according to Eq. (2.48), is l ,<t> - L"P, where <t> (q,) is the proper fun ction and r.o tlw
E proper value. Therefore, using Eq. (3.21) for l .. we obtain

,
'l"""''
E.,(r)
polAmtial ~ih &<f>
'0
= L <fJ
'
where we ha"e set m, ~ L.lf, or L. ~ lII,h. The solution of this equation is <I> = Ce''"'.
where C is the normalization constant. Since the same point of space is repre!:!C.nted by q,
and by q, + 27, it is necessary that <fJ (q,) = <fJ(4) + 2"..), which means that e' .... -
E() E()
;- ei.. !(.+2 ~ 1 ore;2~"1 _ I. This requires that m,
be a po~itive or negative integer; that is,
"" - 0, :I, :2, ... , as indicated previously in Section 3.4 . To determine C, wc apply
the normalization condition, which in this CIlSC becomes J1~<I> .<I> tUb - 1 or

o / , o 1\ I ~ , or, aSiluming C is real, C - I/ V2"... Therefore the normalized proper functions of the
B
V C Z-compon~n t of the angular momentum are

V ... '1>(4)) = . }
v2
i'.,~. 111/ - 0, l , :2, . .. , (3.22)

s-electron (I _ O) '''0 and the proper values L. _ ", .I, are integral multiples of f,.
(.J (oj The square of the magnitude of the angular momentum is given by the operator
l ~ _ l;+ +l; lJ, where lz and L ~ are operators similar to l ., a~ gh'en by Eq. (3.20).
Fig. 3-H. Effect ive potential and radial wave function for 1 - Oand I ;o! 0 for moHon T ransforming to ~pherical coordinateg, by means of an elaborate algebraic manipulation,
under a cen tral force. shows that tJIC square of the angular momentum is represented by the qU:llltum operator

with similar expre$ions for l . and l ~. I~ is more conve nie nt to express t , in te rms of
t 2 ", _,.2 [__ ( ,(.sm9-iJ9') +--
sill e iJO
~
( _.' J.
6in29 iJ4>2
(3.23)
spherical coordinates. Noting from Fig. 3-8 that
The proper equation is l 2 )'(9, "') _ U )'(9, 4, where the proper function , which depends
:I:: _ r sin (J cosq" y _ rsi n (Jsin q" t_rcos9, on the angles fJ lind </1, has been designated by l' (9,q,) and the proper value is f.2. This
corresponds to the rlifferen t ial equation
we have tha t
a axa ay a a~ a
&q, - &q, &x + &q, &y + &q, ih
I
sin9;ij smfJ
(. Of)
ao
I (2)"
+sin29&rp2 + h2J - 0.
/.,2 ,

But &x/iJ<p _ ~ r si n (} sin q, .. - y, ay/&!> - r si n 9 cos q, - x, and az/&q, - O. Therefore It can be shown that to obtain a solution satisfying the reqlLiremenls of quantum
mechanics, it is lIereSil:lry thM 1,2/ ,,2 _ /(1 + 1), where / i ~ a positive integer; that is,

_ _ _ y_+x_,
&q, ax &y
1-0, 1, 2,3, In thi s form we han) obtained the re.~ul lS IJreviously sta.ted in
 ...
3.5) One-fledrau toorejullcliall$ under ulliral jQl"us 131
130 (3.5

Section 3.Sj Ihat is, f.~ _ 1(1 + 1)112. The solutions of the resulting equation,
The term 1-:,. __ i(/ +
I)~~ 2111r2 is n centrifugal potential bccaui'C the corresponding
~force,H,.. _ -aF., .....rar is 1J()~ithe and h('nre is diff'cted allay from the origin.

I
sinO;Ji 8mO
,(. aJ') aI
ao + sin 2 0 iJtr- +
2 }"
1(1+ I )i -0,
,
When we set f:,(r) _ _ Ze2 4nor, II"C obtain a dilfcr('ntial equation that admi!.s as
8OIution~, for ,nolion under coulomb forces, th(' radial funcliolU given in Table 3-6. For
other forms of the IJ()lential energy, dilf('rcnt radial functions rc~ull.
are designated by J' ,., and are the functions given in Table 3-4. The table show!! that
the functions l' '"" lire the products of one factor depending on 0 Imd another depending 1':,'ti."jMl'L,.; 3.6. Rebtivistic correction of the encrgy in hydrogenlikc atoms.
on 4>. [The ct-factor is identical w I~. 3.22.1 That is, i', .., - p~' (cos 0) e'''''. Con- 501,,'io''' .\.'1 lI'e eXlllaincd in Section 2. 12, SchrOdinger'lI (,q uation (3.3) is obtained by
sidering thllt the J' ,., are prolll'f functions of the Olll'ralors L2 and L,. we may then write means of the nonrelati\'istic expression E _ p'lj 2m. + 1-;. This wocedurc is correct
wh('neve,"-the velocity of the electron is \'ery "mall compared "ith the velocity of light.
The lIa[ue of ~j(; for an electron in Il ~tationary ~tate Wall estimated in l~xam]J[e 3.1 and
found to be of the order of , X 1O-3Z/ n. The relll.tivistic elfect due to this velocity,
f; X AMI'I. 1': 3.5. Annlysis of i'chrodingef'~ equalion for motion under central forces. although very small, can easily be detected by speclrOl!copic methods. The relativistic
cnergy of an elcclroll mO\'ing with mom('ntum p tl.nd hailing a potential energy E. (sec
So lutio .. : We reclI\! from I~. (2.9) that Schrodinger's equation for motion with a Eq.A.II)is
potential energy /,', (r) is
H _ n,/m;c2 + p2 + Ii, _ m..c 2,
II'here the r('st ilia')!! energy hll~ been subtracted SO that thc Jcro of energy coincides with
tbe nonreltitiv;sti(" CIl:;(). ,\s~umil\g thnt the monwntUIll p i~ milch smaller than "'oC, we
If we now chll.ngc from the rc~tangu!:\r coordinates I, y, l to the sphericlll coordinlltes may CXIJand the radit"al up to th e ~('cond-ord{'r tl'rm, r\'~ult;ng in
9,4>, thiij equation, afler 1\ lengthy algebraic manipulation, becomes
1 p ~+ ... + r.p
T,
t p-~ - - -
I" " +_ - - ,,""' -
. u
21118 Sm~c~
_I,'
_ _ + __ I [, ,(. ' ) + -I - -,-
I5.mO- , ] ,;
2m ar'l r ar r2 sin 0 a(l iJ8 sin'lO a4>2
+ I';,(r)'" - 1::y,. (3.25)

Re calling Eq. (3. 23) for the operator t 2, we may write

The two t('rm~ insidc the t>3r\'nth(''~ )live th(' nunrelnli\"i~tie BPllTo.~imation for the
I,' (a2
-2111
- a -11t-
-+=r ar
- 'l )
<)
y, +E,.(r)", = EtJ-.
('ne'lt). Therefore theln..;t terlll i~ tilt' fir~t-ordcr n'lati\'ililie correctiolL 10 the IOtnl energy
of the electron, II'hich we ~hllll de,ignate by ,j.f.". Thu~
ar: 2r2

If we set'" _ 1(r) },..,(O,.) lind recogniw that t 'li', .., _ 1(1 + 1)11 21',." the abolle Ip
dE .. - - -

. _ _ _I_ -
Sm!c'l
(p,)(p')
2m.,l;2 2m~
-
2m.
.
equation becomes

d 1(1+ I)] R +
"[d"l + 2_____
___ E,(r)R-ER. The identical termi! inside the I'Ilr\'nthese. corre~IJ()lld to the nOllrelalivistic kinetic
2m dr2 r dr r2 energy of thc electron. So [a.~ a r<'3.onahle al)llro~imalion) lIe may write fOf the first one,
Using the 1"{'8ultof Eqs. (3. 10) al\d (3 .13),
This is lin equation Ihat contains only the radial part R(r) of the wave function tJ-. It is
p~ ~ Zc'l Ze:l Ze2
customary to set R (r } _ I/(r) / r, r<'~ultil1g in -
2m.
- ;111,1'- - - ---
4:11"lu(2r)
+ -- - ---
4no(2r)
4:11"f()l"
- - f.'.

_ ;',:! ~:~ + [E. + /(1 ~:;h2] 'I _ Eu. (3.24 )

This is wmctiU\e~ called tho radial Scllr6d inger equation. Comparing t.hi~ equation with
the onc...:limcnsional Schroding~r equation (2.3), we co nclude that the rndial molioll is
cquivalent to n onc-dimeHliiol1i11 motion under an effective potential energy given by Thu., the rrlalil"i."'t;" {'orr('l"tion is "f Ihr flrd{'l' of (l"r)2 lillle~ the rnrr)!;)" of the electron.
Eq. (3.1!!); that i~, In t!le hyolwlo::('!l I\to'1\, for (,\!llIlple, (~'rl~ i~ "f tlu- urdf'r of 10- .'), !lnd therefore lJ.E. ~
1O -~ ":, or aoont 0.001% of f~', a Iluantily IIhid1, ftlthoul-(h ~"tl\ll, rnn ea.,i!)" be ([ctected
R,.,"" _ 1-:.{r) + /(/ ~,!~/2 . in the laboratory with experimentnl tedllliql/('~ now in u,oc.
132 A/oms with one tltclrOiI (3.6 3.6) Tht Zttman tJJu;1 133
z
To obtain a more prccise result, we notc th!!.! the hut term in Eq. (3.25), which we ha\'c

------~--' , ,,,
just seen is vcry small CQlllpared with ule first two, nl9.y be considered as 9. snl9.11 pertur-
bation. To compute its effect on the 81111i01l9.ry states, we mlly estimate its aVCr:l.gc or
,,\

----~--~
espectation mine, according to Eq. (2.50). Thcrefore in the shile described by the wave
,, --~-

ff)-
function >lt O'M, we havc
, , '_ ~" I.

Ilf:. --~(p) ... -

8m.c
.
Eleevon'8 "'~ '"
motion ( ,
T he resul t of thi~ calculation is ,
t
, ',_
+l~

-0'" ~
,
(3.26)
Equi,,,\enl ~~~
~u rrent ---1-- p

n- , "
whcrc 11/, x
0/ - e'j 4rfofu:. ,., 1/ 137 Fig. 3-15. fu>lation bctll'ccn thc orbital Fig. 3- 16. Precession of the angular mo-
magnetic moment and the angular momen- mentum under the action or a magnetic
is called thefille 8tr uclure COII&talit and IH.I is the absolute value of the energy as givcn by tum of an electron. ficld.
Eq. (3.5). The energy Icvels, ill our approsimstion, are thus given by E - E~ 11/,:,. +
Since thc relatividtic correction (3.26) dcpcnds on I as well as on II, levels having the same
n but different I do not have the !;I1me energy. In othcr words, thc relativistic correction current is opposite to Ull\~ uf t.hc electron motion, reSUlting in an oricntntion of lif t.
destroys the accidental dl'gencracy we found in the case of a coulomb field. Also the which is opposite to that of f" 1'h\18 we may write the vector equation
rdati-'istic correction is always negativc for all nand /. For a gi\'en n, the smaller the value
of I, the larger the rclath'istic oorrection. Thull thc states for which the correction is most M L= --'- L. (3.27)
important in hydrogen are Is and 29. 2me
i\ more refined relativistic theory of thc elcctron has been developed by P. A. .\1. Dira.c. Although we have oblnined this relation for a circulnr orbit and have used elassical
In Dira.c's theory, from the out;jCt, a Schrodingl'r cquation oorre$ponding to the relath'istic
mechanics, this expression still holds true in quantum mechanics for an arbitrary
cnl'rgy is sc~ UII, anll in this way the exact encrgy !lwci:;! are obtaincd. HO"'c\'cr, hi$
theory is tOO complicaler\ to be presenter! ill're. motion with angular momentum L. T he Z-COml}O!\('nt of the urbital magnctie
moment. is
,h
.'J.6 Tht! ZN'",a" A'lff'f'/ ML, 2m. L , -- - -
= --'- - 111,=
2me
(3.28)

Space quantization manifests ilsclf in II. striking way when the electronic molion is
where the quantity
disturbed by fin applied magnetic field. Under a s ufficiently strong magnetic field,
roch spectral line in a onc-clcetron atolll becomes a triplet, consisting of thrC(l
/J1l = "eh """ 0.2732 X IO-H J T - 1 = 5.6564 X
_111. 1O-~ eV T - 1
clogely spaced lines. Tile spacing is the same for all atoms and lines and is pro-
portiollal to the magnitude of tho magnelic field. This efTect was observed for the (3.2')
first time in l80G by the Dutch phy 8 ici~t Picter Zeeman ( 1865- 1943). It has been is called a Bohr maglit/Oll.
named the ZumUlI I'lfed, to honor his work. When a magnetic dipolc of moment M is plnccd in a magnetic field IB, it acquires
An electron describing a cireul9.r orbit with an angular velocity w P:lSSOS each an energy BIB = - M . lB. Thl'rcforc, when an atom is placed in a magnetic field,
I>oint in the orbit w/21f times per second and therefore corresponds to a current the additional energy of an orbiting electron due to the external magnetic field is
I = e{w/2r ). Since the current loop is very small, it is equivalent to a magnetic
dipole whosc magnetic moment is equal to current times area. Thl'rcforc, the
orbital maglle/ic (litJo/e moment of the elcctron is
BIB = - ML
_m.
IB = ..;- L ,m.. (3.30)

At the Mme time, thc electron experiences n t.orque

M /. = e(w/21f)(1fr2) = 1ewr'.
,
Hccalling that for a circular orbit L = lII"t" = lII.,<o.Ir 2, we have 111 L = (e/2m~)L.
This is a relatiOIl betwecn the mngniwdes of M t. and L Now the direction of L is
T = M /. X IB = ~ ~
_m. L x IB ,
related to the direction of motion of the electron, as shown in Fig. 3-15. On the which makes the angular momentum L prcecss around the direction of the magnetic
other hand, the charge of the electron is ncgativl', and therdorc the ccluivalent field IB, as indicated in Fig. 3-Hi. Taking the Z-axis l>arallel to the mllgnetic field IB,

with electron (.1.6 3.7) EI/I"OII spill 135

..
Aloml OIIt

levels corresponding to the orientations of L given by m, ID 2, I, O. The

~ ~~+2
d
t.ransition d -. p now has nine possibilities, according to the selection rule Am, =
-,o 2 l , O. However, transitions corresponding to the same value of AmI all have
the same energy change and therefore yield the same spectral line. We then
conclude that although there are nille possible transitions, the spectrum of the
d - 0 P transition under a magnetic field contains only three lines, with AI' still
given by Eq. (3.32).
The quantiution of angular momentum clearly explains the experimental facts of
the Zeeman effect. If instead of space quantiution, the angular momentum could
have liny orientation, the effect of the magnlltie field would be to broaden each level.
The new levels would then occupy an energy band of width 2~B<RL and each line
,> +, would become a band. This is why, as we mentioned before, the Zeeman effect is a

(.)
-[ 0 +1
'm,
0
m, Y
- , Y0 Y
,., .. -,0

(b)
Fig. 3-17. Splitting or S, P_, Bud d..cnergy lev lll~ undllr the "'Illion of fI.
Thll 8Cpllration of 8ueccssivc levels i~ "'ReB".
we can rewrite Eq. (3.30) as E(JI, = - M L.m or, using Eq. (3.28), we have
We then see that E's, instead of having a continuous range of values, may have
2t+ I distinct values corresponding to each of the 2l +
1 possible oricntations of
L relative to cR, all C<luslly slmcc<l by the amount ~B<R
The total encrgy of an clectron bound to an atom placed in magnetic field is
+
E .. Ell, where 8,. is the cnergy of the clectron's motion in the absence of a
magnetic field. Therefore Eq. (3.31) indicates that each energy level with quantum
numbers 'I l sl>lits into 2l + I levels in the presence of a magnetic field. The
SClmration between successive levcl.s is also reflected in the frequencies a.<IOCiated
with the transitions bctween the Illvels. The situation for S, p-, and dlevels iii
illustrated in Fig. 3- 17. Slates with l = 0 {or s-states) are not affected by lhe
magnetic field. States with l = 1 (or p-states) are split into three C<lually spaced
states, corresponding to orientations in which lnj = + 1, 0, and - I. Thus the
transition p - 0 S becomes a tril)le trtln~ition, one corresponding to 1/11 =- 0 -
ml = 0, with the original frC<lullncy, and two oUlers corresponding to IItl "'"
1 - 0 m, = 0, with Ii. frequency diffllrence given by
.,
proof of space quantization. In fact, the Zeeman effect was one of the phenomena
that prompted introducing the idea of the <Iuantization of angular momentum.
:1.7 Eleclron Spin
magnetic field. Let us recall that the earth, in addition to its orbital motion around the sun, has a
rotational or spinning motion about its axis. Therefore the total angular momen-
tum of the earth is the vector sum of its orbital angular momentum and its spin
angular momentum. By analogy we may suspect that a bound clectron in an atom
is also spinning. However, we cannot describe t.he electron as a spherical spinning
(3.3 ) particle because of our ignorance of its intemal structure. Thus we cannot compute
the spin angular momentum of the electron in the same way that we compute the
spin angular momentum of the earth in terms of its radius and angular velocity.
The idea of electron spin was first proposed in 1926 by C. Uhlenbeck and S. Goud~
smit to explain certain features of the spectra of one-electron atoms (we shall
consider thcsc in Section 3.9). If S is the 'pin angular momentum of an electron
and L is the orbilol angular momentum, the total angular momentum is J = L + 5.
For given values of L and 5, the valueof J depends on their relative oricntation, and
we may expect this to be renected in certain atomic I)roperties; this indeed is the
""".T he existence of electron spin is bonleou~ by a large accumulation of experi.
mental evidence. For example, electron spin is manifested in a very direct way by
the Stern-Gerlach experimellt, first performed in 192-1 . Because the electron is a
charged particle, electron spin should result in an intrins.ie or spin magnetic dipolll
moment fils of the electron. If the electron could be described as a rotating rigid
charged body, the relation bct.wccn IU s and S would be the same as between M t.
and c., as given by Eq. (3.17). However, this is not so, and Wll must write

Ms=-gs -
, S
(3.32) 2me '

So eacll of the single lines p - 0 s shown in Fig. 3-8 becomes three closely spncc<l where gs is called the gyrom.ayl/elic ratio of the electron. The experimental value
lines. Similarly, stalCS with 1 = 2 (or d.statcs) are split into jive equally spaced for gg is 2.0024. For most practical purposes, we can make gs = 2. The total
 ..
136 AlomI with one tkclron (3.7
Addilirm of augular nwmmla 137
magnetic dipole moment of nn orbiting and spinning electron is therefore we then have that s = t and m, = ;. Then z
,
M = M I,+ M s = - -2
m.
(L +QsS), (3.33)
S. = m,lI, 111, = ;.
s= t,
(.... ,)
m.- +t ,,
and, of course, depends not only on the magnitudes of L and S but also on their
relative orientation. The oilly L~'O permitted values of m. (that is, + i and - i), ,
correspondmg to the two possible orientations of S are ", _ 113.1
Suppose now that a beam of hydrogenlike atoms is passed through an inhomo- t->
- ,
.,"1
shown in fig. 3- 1!). For brevity they Me usually rcf~rrcd ,
,,,
geneous magnetic field, as shown in Fig. 3-18. The effect of such a magnetic field
on a magnetic dipole is to exert a force whose dil1!(;tion and magnitude depend on to tI.S spin up ( T) and Bpil! down (1 ), although the spin is
the relative orientation of the magnetic field and the magnetic dipole. For example, neveMaet\ln!ly directed along the Z-axis or opposite to it. ,
if the magnetic dipole is oriented parallel to the magnetic field, it tends to move in
the direction in which the magnetic field increases, while if the magnetic dipole is
oriented antiparnllci to the magnetic field, it will move in the direction in which the
magnetic field decreases. Fig. 3-19. Possible orientations of the 8pin relative to the Z-axis.
--
Spin up
I .We shall designate the wave fWlction associated with the Sz-component of the
$PHl by x .... The exact form of x ... is of 110 concern to us; its mnin propertics are
that
S.x... = m.llx....
~metimes lI"e use. instelld of x"'" the notation x+ and x_. corresponding respee-
tlv e l ~' t~ m. ""' +t and -t. Theil the complete wave function of an electron
mo\'mg 1Il a central field is

>/-.. ''''' .... = R",(r )'I",,(O .;)x ..... (3.35)

Note from &1 (3.35) that. to completely describe the slate of an elcctroll in a
ce~llral field, fo.ur quantum numbers are required: 11, I. m/, and m.

Fig. 3-18. St.crn-Gerlaeh experiment.
In the Stern-Ger!o.eh experiment the inhomogeneous magnetic field is produced
by shaping the pole faecs as shown in Fig. 3-18. The magnetic field illCrcascs in
strength in the &-N direction. If the hydrogenlike atoms are in their groulld state,
the orbital angular momentum of the electron is zero (S-fltatc or I = 0) and the
entire magnetic moment is due to the spin. Therefore the atomic beam will be
deviated by the magnetic field, depending on the orientation of M s, or. which is
c<)uivalent. the orientation of S. The result of the experiment is that the atomic
beam is split. in two by the inhomogeneous magnetic field. This shows that.
the elte/ron 8pin may hlll!t 07tiy two orienlaJions relatitVl 10 the magnetic
field: eiOler parallel or al1tiparallel.
Since. according to our discussion ill Section 3.4, the number of orientations of an
angular momentum vector relative to a fixed Z-axis is 9 = 2l + I. for the case of
spin we have the value fI = 2 or 1 = 1. Designating the spin quantum number by
s instead of I and the quantum number corresponding to the component S, by moo
. The prol)CrtlCS of the electron spin. deseribcd by &1. (3.3'1). cannot be cxplained
m te~s of any classical model of the electron. However, we can cxplnin them
theoret l~.lly when. we combine the ideas of quantum mechanics with the principle
o~ relatlVl.ty. ThIS was done by Dirac around 1928, but we shall not diseuss
Jus analYSIS here. since it is beyond the SCOI>C of this book.
'~'h~n the atom is in a state in which I rf. 0, the spl iuing produced by the mag-
netiC held depends on the total magnetic moment, or- which i~ the same thing-
011 the total angular momentum J = l~ +
S. Therefore the Stem-Gerlach experi-
Illcntean be used to determine the total Angular momentum of the stale of a.n atom.
:J.ll A""itlo" o( jt"""'ur .tlo"''''''tI
In the pre
. VIus0
section we SUII' t ,lut the resul tan t angular momentum 1 of an
cleet~n m a hydrogenlike atOll} is the s um of the orbital angular momentum I. and
Ihe ~pm angular momentum S ; that is, J = L +
S. It is important to examine the
posslblc values of J acco n:l ing to quantum mechanies. So Ihat our analysis may be
generally applicable, let us suppose that we have two angular momenta designated
by J land 1 2, which may, lor example, correspond to the orbital angUla,'molllentum

(3.8
138 3.9) Spin-orbit inl~raclioo 139

of an electron and its spill (as we have just considered in the p.reeeding section).. or
the angular momentum of two elec:t r~ns in an alom (a C!I.8C wlllc\w~ B~al.l eonsld~r
TADLE 3-7 Des i!!,,1I 1io n o f El ee lroni c Stin e
in the next chaptcr). T hen J~ = )d)1 + l)h 2 ,J I~ = m,h, 1l~ld J ~ -:- )~(i2 ~)h , + 0 2 3
J 2. = 11I2h. It can be shown that ill the most general case 11 ~nd 12 can be Cll~er
integers or half integers; that is, 0, !, I, 4, 2, . .. As explained before, orbItal
angular momenta can only be integers.
Ir J = J , + 12 is the resultant angular momentum, so that. J. = J I. J 2" +
j

Symbol

11112 PI I~ P 312 d,n d$n
! t
, ~,
t
'm
then
J. = IIlh, m= i, (i - I), . . . (3.36) A~anothc r illustration , ifi2 = 1 andil ~ 1, thenj = il I,i, oril - 1. It +
mllY be spown that in an electric dipole transition the photon carries an lI.ngular
with 111 = ml + m2. But because 1, and 12 may have different relative orienta- momentum corresponding to ai-value of 1. Then if il refers to the orbital angular
tions, there are several possible values of J . Thus we .find I.hat the qu~ntum nu~ momentum 1 of the electron and 12 = I to that of the photon, the allowed values
+
ber i varies in unit-sized steps from i l h down 10 111 -121,80 that It can attam of the orbital angular momentum of an electron after emitting or absorbing the
only the values photo n are 1 + 1, I, and 1 - I, corresponding to 6l = l , O. As we explained
previously in Section 3.4, 6l = 0 is ruled out by parity considerations.
il +:h - I, il +i2 - 2, ... , Iii-hi
T he first value corresl>onds to 1 , and 12 "parnl!el ~ and the last val ue to. the tw.o
:,.!~ .fiJpln-Orhlt Inter"~ilon
angular momenta "antiparnllel." . S.u.c~CS8.ive :values of i dilTer by one Ulllt, and If
h 5. ii, the total number of poISSlbliItlCS IS 212 + l. The double orientation of the electron SIJin relative to the orbital angular momen-
S tum gives rise to an important clTect: the doubling of energy levels (except s-Ievels)
J of hydrogenlike atoms. This doubling of levels in tunl gives rise to a doubling of
/,
the spectral lines. These lines appear in pairs, having frequencies or wavelengths
which are very close and arc therefore called doublets. T he bcst.-known doublet is
that comL}Qscd of the two yellow or D-linesof sodium, corresponding to wavelengths
of 5890 A and 5896 A. In fact, it was the problem of explaining these doublets
which first gave rise to the idea of an electron spin with two possible orientations.
The doubling of the energy levels is a consequence of the so-called *pin-<ffbit
Fig. 3-2{). POMiblc r('lath'e orientations interaction. The origin of this interaction is as follows: in a frame of reference X}'Z
of L and S, when I - 2. attached to the nucleus of an atom, the electron appears to revolve around the
nucleus (Fig. 3-2 Ia) with angula r momentum L. But, in a frame of reference
j .. ,+~ (spin up) j_I_! (spin do,,''')
X' Y'Z ' attached to the electron it is the' nucleus which appears to revolve around
(0) (b)

for example, if h = ;, the possible values of i are ~I + ; and il - ;, cor- z Z'

responding to parallel and antiparal!el orientations. Thus, In the case of an electron,
if 1 , = L and 12 so; S, we have that the possible values of th~ to~1 angular
momentum 1 are j _ 1 ;. These two situations are illustrated 111 FIg. 3-20 for L L

r:1~
~--)'
I = 2. H ence we have that
the electron spin mal/have only two pwsible orientatiolls relative to the
~-- y
orbital angular momentUltL.
/ -,
When 1 = 0 (or s-stale) only i = ; is possible. When we indicate the .value of i
as a subscript, the possible states of an electron in a central field are dcslgnated as
x
,.) X'
'")
shown in Table 3-7. Fig. 3-21. Origin of the spin-orbit interaction.

MfJ 3.9) Spin-orbi/ ili/UtldiOfI

the electron. The nucleus, since it has a positive charge, produce!! a magnetic field
1- 0
IB in the X' J"Z' frame which is parallel to the angular mo mentum L. Since the
elcctron is n~ rest rellllive to X'J"Z'. the only inlCr.l.ctioll of the nuclear mngnetic
field is with the electron-spin magnetic moment M s. This intcrcction is propor*
._3---;',,'~~-
tionnl to !tI $ &. But <B is Imrallcl to L and ill s is parallel to S. T herefore the
interaction is proportionsl to S L. This is why this effect is called sllin-orbit
inte mction. We may then write, for the energy of the electron due to the spin.
orbit intcmotion, Fig. 3-22. Spin-orbit splitting of encrgy
levels ,and possible traneitione. The da.sbed
ESL = as L , (3.37) line indicates R trl1nsition with \'ery 10.....
p, ~

probability:
where a is a (IUantity which depends on the different variables affecting the
cJcclron's motion and whose Inccise form we need not know nt this time. Given
that En is the onergy of the electronic motion, iLSSuming only a centra! foree, then
the total energy, when the IIpin-orbit interaction is added, is
EX"MII'U'; 3.i . Calculation of the scllaralion of 111'0 energy levels due to the 8pin-orbit
interaction.
E = E" + Bsf. = E" + as L . (3.38)
~/"' iQlI : Our [}Urt>osc i.s to. colllpute the value of Est. for the two cases of spin lip and
When we write this expression we assume that the spi n-orbit interaction docs not
IIp~n down, and ~nd their difference. 1~his difference gives the splilling of the energy
nlTect. the contribution to the energy due to the central forees, II. valid assumption leI elIJ. To do th,s, "'e must find S L III both cues. Now J _ L +
S and therefore
so long llS E s1. is very small compared with E". For a given value of L and S, the + +
p - l ."l 52 25. I " frOIll which we obtain
8pin-orbit interaction E Sf. depends on t.he relative orientation of these two vectors.
But since S can have only two possible orielitatiOlls relative to I., we conclude that 5 L _ i (P _ 1,2 - 52).

the 8pin-orbit ill/eraction lip/its each elec/ron f:.ttergy level with a yit'eII !~:~~,ing the I'alues of 1"2, 52, I1nd p , as given by Eqs. (3.15), (3.34), and (3.36), we
l'()l~ oj i il1/o two douly 8wu;cd iel'(!i.,.
S L - Hi(j + I) - 1(1 + I) - i:,.,2
One level COrW.iI>Ollds to L and S parallel or spin UI) U ::::I 1+ !), and thc other to L
nnd S antilmrallel or spin down U = l - i). Obviously s-levels (I = 0) remain spin up,j _ l + !,
singlc. spin down, i - I - i.
In the presence of a spin-orbit. interaction the qunlltum numbers needed to Thus, when we usc Eq. (3.38), the ellergy lel'els become
specify the angular momcntum state of an clectron arc /, j, and m, where III refers
to the proper wl.lue of J z. The selection rules for electric-dipole trnnsitions re- E( T) - E. + f. S t ( T) h'. + io1,.,2, j - 1 + i,
quired by the conservatioll of angular momcntum are E( 1) - E. + HISL ( 1 ) - E. - io(1 + 1)112, j -I-i.
tll = I, tl j = 0, l, tlm = 0, 1. (3.39) ~h l.ls~ if 0 is positive, le:'c1s with i ~ 1+ 1- are slightly raised and those wilh j _ 1 - !
.re ahghtly lowered relative to the central force energy level E . To complete our calcula-
T he transitions with tlj = 0 are very weak becnusc thcy require a reversal of the tlOIl ":e ~ust e\'sluate 11, but silloo this calculation is beyond the level of this book, we
direction of the spin relative to the orbital angular momentum of the electron. shall hmlt ou~h'es to Ilroducillg the final result, which is
Bill. the foree that would I)ro<iuce such spin reversal is the spin-orbit intcrnction,
which is a rclativ{'\y weak foree.
Figure 3- 22 depicts (not to scale) how the levels showll ill r,'ig. 3-7 are alTected
o ~ h2nt{/ + I){/ + !) ,
by the spin-orbit interaction, and some of the IXlSSible transitions. T he relatively whe re Q" 18
tlfi
Ie Ine structure constant, .Introduced ill EXl1mple 3.6, and 11<.'.1 is the absolute
weak transition d 312 --> P 3I2 is indicated by a dashed line. We see that spcctrnl val~e of the e~ergy of the cl~tron in lhe absence of spin-orbit interaetion.
lilies corresponding to trnnsitions betwccn s- and p-levels arc therefore doublets, 1 he separalion bet"'cen the two energy levels is
while those betwccn d- and I>-Icvels arc tril)lel.8, although one of the lines is SO weak
that one may speak of a doublel. tlEsf. - 1-tlh2(2/ + 1) _IE'. IZ'-' ... 5.32 X 10-'\ 1.c.
u IZ'
nl(/ 1) + n/(l I) +

AIOI1U with OIIe ellron (3.9 3~) Spin-bil inluodiM

Thus the separation bet\\'een the levels due to the Silin.orbit intersction is very small
eompsred with If:.I, and decreases a~ 11 and I increa.se. For examille, for the 2p-state in
hydrogen, AEsl. i8 about '1.6 X 10 - 6 eV. So the transition from the 2p-state to the Is-
atate should COIlJlistof two lines separated in frequency by an amount 1.11 X LOIO HI or a
wa\'elength difference of about 5.3 X 10- 13 m. Thel!e values should be compared with the
frequency 2.47 X LOIS H ~ and the wavelength 1.21 X 10- 7 m eorre~ pon ding to the
transition in the absence of the .11l1in-orbit interaction.
Solution : The spin-orbit in teraction ESL .. as . L depends on the relative orienta-
tion of 5 and L ; that ill., on the angle formed by these two angular momenta. But when the
potential energy depends on an angle, a torque is applied in a direction perpendicular to
the angle. Thus a torque exists perpendicular to 5 and L which makes these vectors
preceM. HO'll,.ever, if no external torques are applied, the total angular momentum
} - IJ+ S must be constant. So we may visuali ~e the effect of the spin-orbi t interaction
as producing a precellllion of 5 and L around their resultant, as indicated in Fig, 3-25.

,,t
s
j
, SlntC$
d",
0,036 rrn- t
" , I'm.dm Fig. 3-25.
moment,
Resultant average magnetic
,,
,
0.11 =-1 L
0, , $I/2,PI/2

The magne ti c dipole moment of the electron, with fill ... 2, is given in Eq. (3.33) by
j

i i ,If - -(t/2m.,( L + 2S) - -(e/2m.) (J + S)

"3/2
and is not directly opposed to J. Therefore M is also precessing around J. The average
value of M is equal to the componen t of {If parallel to J. So we may lI'rite

,.,
where U J is the uniL 'ector in the direction of J, which may be written as U J _ } / J.
Therefore
,If... _ -(t/2m., (J +
S). J }/J~ _ -(e/2m.,(1 +
5 ) / JZ) .
\ - - -__-'-_...L--'- o, J $1/2, PI/2 Since ) .. L + +
5, lI'e may write 5 ) _ ; () 2 5{l - L~. ThUll, when we replace the
squares of the angular momenta by their quantal e){pression~, we finally have
Fig. 3-23. Fine structure of the n _ 3 ...... n _ 2 Fig_ 3-2 1, Spliltingofthen _ 2lcvel
transition in hydrogen. in hyd rogen, ineluding the Lamb shift. M.~. _ -(e/2m"fI) ,
where
_ 1+ 5' ) _ +j(j+I)+.(.+ I )-I(I+ I )
When the relativistic correction given by Eq . (3.26) i.ll added to the spin-orbit inter- (3.40)
fI J2 1 2j(j+ l )
action, the energy levels are gil'en, up 10 the first.order approxima tion, by the ex])ression
is called the iA.w1~ f(Jd()1. Its values for spin up and 8])in down are
B'. + If:. IZ
2 2
Jo: _ a ( -"- _ -,- ' - ) , I
n 4n J+; fI- 1 21 + 1 ' (3.41)

/md thus levels with the same /1. and i coincide. Lel'el n .. I has j - t
only and remains
single. Energy levels for n .. 2 and n _ 3 and the allowed transitions among these levels
are shown in Fig. 3-23 for hydrogen. :\ Iore careful measurements and more I'recise
calculations show that states with different I but the sallie i do not coincide, but in fact
arc slightly separated. For example, the Il.ctuallevel arrll.ngementfor n .. 2 is 113 shown in
.'ig. 3-24 for hydrogen. The separation between the S II2 and the JlII2 levels is called th e
l"omb $hifl,
XAMP'JE J .8. Calculation of the magnetic moment of an electron in the presence of
Spin-orbit interaction.
In the presence of a lI'eak magnetic field which does not appreciably disturb the dynam-
ical relations of Fig. 3- 25, the interaction energy is
(3.42)
This l"C3ults in more complicated Zeeman rmUerns than those considered in Section 3.6.
The Zeeman effect, as given by Eq. (3,42), is very important because it allo,,'s us to find,
experimentally and from it verify the values of i and I for the electron's atate. The results
of Section 3.6 are still valid lI'hen the magnetic field is strong, SO that t he magnetic inter-
action is much larger than the spin-orbit interaction and the latter can be ignored,

Problerru 145
AIO/7I.I wilh onll tlllelron

3.7 Show that for a photon wc may use augular walle function~ p~, p~, and p~ and
the equivalence!! 1 eV .. 8065.8 cm- I and compare result~.
I cm- I .. 1.2398 X 10-4 eV. 3.14 Referring to the definition of the
I. "Papers Gillen at the Niels Bohr Memorial Sesliion:' A. Bohr, F. Bloch, J. Neilson,
J . Rosenfeld, V. Weisskopf, lllld J . Wheeler, Phyric. TodGy, October 1963, page 22 3.8 Suppose that you were repeating the associated Legend re functions in Problem
Franck- Hcrta experimcnt, using atomie 3.10, ehow that their parity is equal lO
2. "The Ellolution or the Balmer Series, B L. Banet, Am. J. Phy" 3 496 (1966) (- 1)1+-. [/lint: Note "'hat hapl)Cns when
hydrogen as the "apor. What lines in the
3. "Orbital Angular Momentum in Quantum l\lechanics," M. Whippman, Am. J. Phil', hydrogen spectrum .... ould you obaen'c if ~ is replaced by -t in the definitions of
M. 6S6 (1966) the maximum energy of the electrons was 1)1a> and I)~W.I
4. "A Quantum-Dynamical Dllscrilllion of Atoms and Radiatille PrOCCS'le!l, n G. Fowles, 12.5 eV? 3.15 In III,herical coordinates, the parity
.'I m. J. Phy" 31, 407 (1963) 3.9 (a) Usi ng the mcthod of Examplc 3.1, OI)Cration r ..... - r (or 2:, 1/, z ..... -x, -1/,
S. E~III.. oJ W(lI//l Mechanic., N. Mott. Cambridge: Cambridge Unillersity Prt8ll, complite the frequency of the circular -z) is eXllresscd by the transformaticrn
1962, Chapter 4, Section~ 4- 13; Chapter 5, Sections 1.2.1 and 4.3 motion of an electron in a hydrogen atom r,8,4> ..... r, ... - 0, ... + 4>. Analyzethe
in the level corresponding to quantum behavior of the angular walle functions
6. Pri7ldplt. oJ Modern Phyric., R . Leighton. New York : McGraw-Hill, 1959, Cha pters
number n. (b) Compute the frequency of given in Table 3-4 and confi rm the rule
5 and 6
the radiation emitted in the transilion from given in the text that the parity of the
7. tUomic Splro and Atomic Strllct\.lre, G . Herzberg. New York: Dover, 1951 , Challter 1 sta te n to state n - 1. (c) Show that the 1'1'"1 fu nctions is (_ I}I. Repeat for the
8. Tht Bt havior oj EltetrOM i n tllom ., R. HochsttllSSCr. New York: llenjamin, 1964 rC!lults of (a) and (b) agree when n is lIery wavc functions appearing in Table 3-5.
9. S tructyre oj Motter, W. Finkelnburg. New York: Academic Prcss, 1964, Chapter 3 large. 3.16 (a) Show that the angular wave
10. Quom u"l Thwry oJ Matter, J. (. Slater. New York: McGraw-Hill, 1951 , Chapter 5 3.10 We can compute the angular momen- fUIl{)(ions of Table 3- 5 may be obtained by
tum wal'c functions J', .. (O, 4 by using the a prol)Cr linear combination of the wave
11. Introduction /0 Mooern Ph l/ricl, R. Hichtmyer, E. Kennard, and T. Lauril$en. New
cxpression }fl . . . . N,,,,Pj (cos O)t;"', where fu nctions in Table 3-4. (b) Exprcss the
York : McGraw-Hill, 1955, Chapter 5, Sections 80-83; Chapter 6, Sections 104- 108
wave fu nctions of Table 3-5 in termll of
21+ 1 (1 - m)! ::t, y, I, and r and justify the notation used
/1',....
~ (I+m)! for their descrilltion.
Proble m. is the normalization constant and ' )j(D is 3. 17 Express the operators l ~ and l . in
the IJ880Cimtd l.tgffldre J unchon , defined by spherical coordinates. U~ing these values,
3.1 Calculate the angular "clocity and the pare these numbel'3 with ule number of together with Eq. (3. 2 1) for l ., obtain
potential and kinetic energiee of the orbits the earth has made around the 8un e~pre!!Sjon (3.23) for l 2.
(-1)"0 _ E2).12 aP,CE)
electron in a hydrogcn atom as a function
of the quantum number n, assumi ng that
in its 2 X 1011 yeal'3 of existence.
3.4 Five lines in the Bahner series of
dr 3. 18 Write the radial equation (3.24) for a
free l)!I rlicie (E. - 0). Show, by direct
the electron movcs in circular orbits (see hydrogen have the wavelengths 3669.42 A, substitution into the equation , that the
Example 3. 1). Evaluate the numerical 3770.06 A, 3835.40 A, 3970.07 A, and I d' I IIOlutions for I .. 0 and I .. 1 satisfying the
P ICE)" - -(E2-1)
coeffidenu. Plot the calculated lIalues II.!! 4340.47 .t Plot jj agaillllt n for the Balmer 211! d~1 requircmcnt that \.I .. 0 for r .. 0 are " -
functions of " to determine thei r trend as series. By inspedion, find the IIIIlue of n sin fer and" .. (sin fer)/fer - cos fer, where
are the ugendre pol!f1lomiolll. Compute
the total energy of the electron in cre~. of the upper level for each or the five wave- fe2 .. 2mE/ fa 2. Write the complete free
3.2 Find the recoil energy and recoil lengths ghen. r l .. for I .. 0, I, and 2 and COnll)!lre with pa rticle IIOl ution ofl .. (r), including the
the cxpressions given in Table 3-4.
"elocity of a hydrogen alom whcn it ~ uf 3.5 Compute the wallelength difference angular part, for 1 .. 0 and I .. I. Inter-
fcrs a transition from the state n .. 4 to 3.11 Show that, according to their defini- pret the walle funclion i - 0 as a combina-
between the Ha (that is, n .. 3 to n .. 2)
the state ft .. 1, emitting a I)holon. From tion (sec Problem 3.10), the i.t:gendre tion of an incoming and an outgoing
li nes of hydroge n, deuterium, and tritium
t he result, justify the lIalidity of the as- IlOlynomials are of degree I and contain spherical wave. [Note: It can be shown
which results from the ma.sa differen ce of
sumption that we made when we wrote only even or odd IlOwers of ~ Ill! I is evcn that the general wave ~un ction for a frcc
th ese atoms.
Eq. (3. \4) . or odd. particlc of momentum p" flk and
3.6 Which of the lines of the spectrum of
3.12 By direct ca1culatlon, determine orbital angular momentum 1. _
3.3 If thc allcrage lifetime of tin excited
state of hyd rogen ie of t he order of IO- s 5,
esti mate how many orbits an electron
hydrogen fall in the lIisible region of the
spcctrum (between 4000 A and 7000 A).
Which lines of He + fall in the same region?
whether Ole wave functions appearing in
Tablc 3- 5 are proper fun ctions of the
~ 'I is "'I. " h(kr) Yr .(O, 4 ,
where j I(kr} is called the ~pherical Bessel
makee (a) when it i& in the atale n .. 2 and How could you distinguish whether therc operatol'3 (a) t .. (b) l~. Junction of order I. The student should
(b) whcn it is in the Btate n .. 15, before it WWl hydrogen mixed in .... ith a helium 3. 13 l\b ke a polar diagram of lJ'I'"rl~ for consult a mathematical handbook to
suffeT!! a transition to state n .. 1. (c) Com- sample? I .. I and ml _ 0, l. Repeat for the investigate the Iksscl functions and obtain

146 A/om" with om dulron
jo(kr) andh(kr) , comparing these with the
results obtained in the first part of t.his
problem.]
3.19 It can be shown that the wave
function for a (ree particle moving along
the Z-axis with momentum Ilk may be
expressed as
- L:iIV'h-{21+ i)jdkr)YIO(8).
, 3.24 Verify that the angular momentum
Why are only ml - 0 wave functions
allowed? Why docs the solution contain
many angular momentum {unctions? Write
the first two terms in the su mmation in fulL
(See the previous problem for the definition
of jd
3.20 The radial wave function6 for the
hydrogen atom are given by
where p - 2Zr/ nao , the L: 8rc the ag~oci
aled lAguerre polynomiab, which are de-
fined 115
L:(P) _ .!.... [L,(P)] ,
dP'
where
, oJ.- by its expression (3.18) and inlegraw over
L,(p) - e'~ [p'e- P ],
d,
and N . 1 is the normalization constant given
by
[( 2Z)' (" - ,- I)']'"
N., - - 1100 2n[(n +l)!j3
Write all the radial functions for n - 1,2,
and 3, and compare with the expressions
given in Table 3-6.
3.21 Show that the associawd Laguerre
polynomials, defined in Problem 3.20, are
of degree t - 8. This shows that 8 ~ I.
Thus verify the rule that for a given 11. the
maximum value of I is n - I.
..
3.22 From the informat ion given in
Problem 3.20, show that the radial wave
functions for hydrogen behave as pi for
small values of r and that they behave as
p e-12 for large values of T.
ft
Therefore
conclude th at the larger the value of I, the
less l)enetratiug the orbit.
3.23 Show, by dire ct substitution, that
RI() is a s()lution of SchrOdinger's radial
equation.
wave functions Y 1.. ,(0, <1 given in Table
3-4 are orthogonal and normalized. (The
condition of orthogonality and normaliza-
tion is that
where dfI - sin 0 d8 do; and ~~b is I if a - b,
and zero otherwise.)
3.25 The volume element in spherical
coordinates (Fig. 3- 26) is
dV _ drdS _ r 2 drdll.
T he probability of finding an elcttron
within that vol ume element is loJ.- I2 r t de dfI.
Verify that the probability of finding the
electron within the spherical shell of radii r
+
and r dr, regardless of the angular posi-
tion, is given by 1R 0112r2 dr. [Hint: Replace
all angles, using the normaliz!l.tion tondi-
lion for r 1"1 given in Problem 3.24.]
z na tes is proportional to e:l:'" Ir, where
y oorrection AE.I E. for the n ~ 2 ene rgy
x Figure 3-26
3.26 Using the result of the preceding
problem, find (a) the most probable dis-
tanee, and (b) the average distanee of the
electron from the proton in the l s-s tate in
hydrogen. Compare with the Bohr radius
of the orbit wh en n - I.
3.27 (a) Us ing the volume element given
in Problem 3.25, sho w that the normaliza_
tion condition of the oJ.-OI" 1 wave functions
requires that fOlRftllzrz dr - I. (b) Re-
ferring ~ Fig. 3-13, show that the area
under each curve is equal t() one, as
required by the normalization condition.
[/lint: Consider each lobe as a triangle.]
3.28 The average value of T in the
hydrogen like atoms is given by
Compute r. v fo r all staws with n _ I, 2,
and 3. Compare these values with the
corresponding \3ohr radii. Using f .... as a
measure of the Hire of the orbit, arrange the
nl staws according to increasing average
distan ces from the nucleus.
3.29 The radial wave functions have one
or more nodes, i.e., regions in which the
probability of finding the electron is zero.
F ind the value of r at which this happens
for the 2s-wave function in Table 3-6.
3.30 Using Eq. (3.24), show that., regard_
less of the value of the angular momentum,
the radial wave function of a free particle at
large distances from the origin of coordi-
k 2 _ 2mE.'l hz. Hence the complete wave
function can be written as f(O )eUo'lr ,
where 1(0) depends on the angular momen-
tum. Interpret both signs.
3.3t Write the radial and an gular inwgrals
required to tompuw the matrix clements of
Z - r cos 0 between states nlml and n'l'm'.
Show that the matrix elements are zero
unless ml _ mi.
3.32 Estimate the fractional relativistic
levels in the hydrogen atom.
Probkms 147
3.33 Analyze t.he splitting of p-, d-, and
f-levels of a one-clectron atom as a result of
the relativisti c effect. [llint: See Example
3.6.]
3.34 Determine the electric current. of the
electron in the first three Hohr orbi t.s
(11. - 1,2,3) . Also calculate the magnetic
dipole moment of tile electron for each case.
3.35 Draw an encrgy-levcl diagram for the
41- and 3d-slates of hydrogen in the prcs-
ence of a magnetic field. Show that in the
41 ...... 3d trall8ition, the number of spectral
lines is three. If the magnetic field is 0.5 T ,
would the lines be observable, given that
the resol ution of a spectrometer is 10 - 11 m?
3.36 The value of tim. may be obtained
uperimentally by observing the 7..ccman
effect. Find the value of tim. if the separa-
tion between two lines in a field of 0.450 T
is 0.629 X lOw Hz. What is the wave-
length separation for the hyd rogen line in
the transition n _ 2 to n _ I? Is the
wavelength separati on for the H" line
(11. - 3 to n - 2) greawr than, less than,
or the same?
3.37 The force exerted on a magnetic
dipole of moment M by an inhomogenous
magnetic field <B of gradient d<Bl dz is
F _ M(dfl tk). Givcn that the gradi-
entinacertain region is 1.5 X 10~Tm - l,
calculate the force exerted on an electron
due to its spin magnetic dipole momcnt. If
a hydrogen atom moves I m in a direction
perpendicular to such a field, calculate the
vertical displacement, given that the
velocity of the hydrogen atom is 10 5 m S-I
and the electron spin is either parallel or
antipara!lel to the magnetic field.
3.38 A beam of Silver atoms with an
average velocity of 7 X 10 2 m S-I passes
through an inhomogenous magnetic field
0.1 m long which has a gradient of 3 X 102
T m - I in a direction perpend icular to the
motion of the atoms. Find the maximum
separation of the two beams which emerge
from the field region. Assume th!l.t the net
magnetic moment of each atom is I Bohr
magneton.
 p

148 Atonu with one eledron

4
3.39 What ra.d.iofreque ncy signal will in-
duce electron spin transitions to chsnge
from parallel to antiparalle\ orientation (or
3045 For a relath"istie particle moving in a
region of potential energy E., the total
energy is written E - cv'm~~ p: + + E".
ATOMS WITH MANY
vice versa) in a magnetic field of 10- 1 1'?
3.40 Usi ng I~. (3.39) \erify that the
This may al.so 00 written as (E - Hp J2 -
m~4 + p2c2. Write the corresp.o ndin g
ELECTRONS
numOOI"ll !ivcn for the ~pin-orbit Slllitting Sehr6dinger equation for the hydrogen
of the energy levels for hydrogen shown in atom by replacing p with LLII operator
Fig. 3-23 are correct. Calculate Ihe !lame -i.hV (see Problem 3.44) . [Note: This
splitting energies for Ile+. equation does not give the correct relativi&-
3.41 It Wall indicated in Example 3.8 that ti c energy le\"els of hydrogen.J
the Bpin-orbit interaction causes a preces- 3.46 It can be I:Iho""n that the spin-orbit
sion of I. and S about their resultant ) , interaction is
whi ch is constant. Show that, in this C/l.llC,
Est. _ -1- -1 -dE. So L
L, and S. cannot have well-defined values 2m!c 2 r dr '
cven though their 8um J . is constant.
Con!lequently, ml and m. arc not good where t:, is the potential energy due to the
quantum numbers, while m is a good eleetrie interaction with the nucleus. Using
number. the result th at
3.42 Analyze the splitting of the 3d-level
Z'
in hydrogen due to a magnetiC field (a) (,~,., - ~n31(1+1)(l+ I) '
when the magnetic field is weak and (b)
whcn it is strong, compared with the spin-
obtain the expression for the spi n-orbit
orbit interaction.
spliuing, /lEn, gi\"en in Example 3.7.
3.43 Discuss the Sillitting of the lines in
3.47 :\ ccordillg to Example 3.6, the
the 3d ..... 21) transition in the presence of a
relativistic correction to tJle energy levels
magnetic field, when the magnetic field is
in a one-electron atom can be obtained by
"eak compared with the S]lin-orbit inter-
com]luting the average value of
action.
3.44 The relativistic expression for the
energy of a free IlArticle is f.'2 _ m~~ +
p 2 C2 . Write the corresponding relativistic \\"here E. is ,i\en by Balmer's formula and
Schrl'K!inger equation, by replacing p with 1-:, - -Z~2/4nor is the potential energy 4.1 Introduction
illl operator - ihV (according to Table 2- 4). of the electron. Using the results
4.2 The HeLium Atom
This equation is cal\e(1 t he Jo.:lei~Gord()n
tqlltt/ion. (a) Find the IIOlu tioll correspond- r
( _ ')
.... _ _Z_, 4.3 The Exclusion Principle
ing to a free particle moving along the 'On
4.4 Eleclro,~ic Structure oj Atoms
X-axi!). (b) Show that for a free particle
with zero angular momentum the ""ave 4.5 &S Coupling
( _') Z'
function is 1/1 _ Ce-/r, where .. - moe/Ii , ... -a.~n3(1+!) 4.6 Atoms wilh One or Two Valence Eleclrons
is 2... times the reciprocal of the Compton
wavelength of the particle. obtain }o:q. {3.26J. 4.7 X-Ray Spectra
 po ,
151) A /onu lDiLII /IUUIy tkdrom (4.2 Q.2) The he/hun alom 151

4.1 ,,,trod_eil.,, The first two te mlS correspond to the attraction between the nucleus and cach of
the electrons and the last term to the repulsion between the two electrons. Even
All atoms-e)(cept. hydrogen and certain ions of the light elements-eontain several for thi8 relatively simple problem of only two electrons, it is impossible to solve
electrolls. Therefore it may seem that the one-electron problem studied in the pre- Schrodinger's equation exactly; it is necessary to make several approximations.
vious chapter is of little practical value. However, an understanding of the proper- Since the mathematical discussion of heliumlike atoms is beyond the scope of t.his
ties of one-electron atoms is very helpful in analyzing many-clectron atoms. book, we ~hal1limit ourselves to a physical description, followed, in Example 4.2,
The first difficulty with the many.-elcctroll atom is the impossibility of describing by a bricf explanation of how the energy is calculated.
the motion of each individual electron because, in addition to considering the elec- As a first approximation, we may ignore the last term (or the electron-clectron
trical interaction of each electron with the nucleus, we must consider the mutual interaction tenn) in Eq. (4.2). This is equivalent to assuming that each electron
interactions among the electrons. Thus the potential energy of the whole atom is moves independently of the other. Thu8 we ma.y call this approximation the
inkpenMnt-part.icle nwdel. Therefore the motion of each electron can be described
-~+ L: -,-'-. (4. 1) by hydrogenlike wave functions of the type ,y~I"', = R~I ( r)Y,_,(B, 41), spooified by
4'J1"foT. All 4..-EgTij
po.in
the orbital quantum numbers II, I, m,. The energy of the atom is obtained by add-
ing tenns of the fonn of Eq. (3.5), that is, B = -RhcZ 2 Jn 2 , one for each electron.
The last summation provides a coupling in the motion of the electrons, and hence Hence in the case of He, the energy of the electronic motion in ~he ground state,
we cannot consider each electron as moving independently of the others. Any ,~ = 1 (if we setZ = 2in Eq. 3.5) would beEue = 2 X (-54.4eV):: - IOS.8eV.
modification in the motion of one electron must, of necessity, affect the motiOll of The experimental value, however, is Ene = - 78.98 eV. Thus our first-order
all t he other electrons. Therefore we cannot speak of the individual energy of each approximation gives an energy which is too low. T he reason for this is that we
electron but only of the cnergy of t.he whole atom (or ion). For the same reason, neglected the repulsion of t.he I.wo electrons, which tends to raise the energy of the
wc do not. speak of a wave function for each electron, but only a wave function for atom.
the complete atom. We can improve our approximation by considering lhe perturbalioll of the elec-
The problcm of many eledrons cannot be solved exactly; therefore certain ap- tro/lie motion caused by the mutual intemction of the two electrons. A plausible
proximations are required. We shall illustrate these approximations by discussing improvement is to consider that each electron moves not only in the central field
the helium atom. of the nucleus but also in an OIJI!rage centml field produced by the other electron.
Thus the apparent net effect of each electron on the motion of the other is to screen
the charge of the nucleus by a certain amount. The energy of the atom in the
ground state may thcn be written as
E = 2(Z - $)'E II ,
where E'II = - 13.6 e V (the energy for hydrogenlike motion) and S is the screening
Fig. 4-1. A heliumlike arom or ion. constant, which for the ground state of helium must have the value of 0.32 to agree
with the observed value of E ll e. That is, the screening effect of each electron on the
other is equivalent to about one-third of the electronic charge.
As an aid, let us label the electrons 1 and 2. Since in our first approximation we
assumed that the electrons moved independently, the probahility of finding elec-
tron ! at a givell position and at the same time finding electron 2 at. another given
4.2 Tlte l'e'I",.. Ato,.. position is the IJroduct of the probability distribntion for each electron, because
Of all the many-electron atoms, the simplest are those with two electrons, such as the two event-s are uncorrclated ; that is, p.t.om = P( I )P(2). Therefore we con-
the negative hydrogen ion H - (Z = 1), t he helium atom He (Z = 2), the singly clude that in the independent-particle model the wave fun ction of the atom should
ionized lithium atom Li+ (Z = 3), and 110 on. The potential energy of the elec- be the !Haduct of the wave functions for each electron. If we designate the orbital
quantum numbers n.lm, of electron I by a and the quantum numbers of electron 2
tron8 in this case (Fig. 4-1) is
This is also a straightforward eol\clu~ion from Schrodinger's cql.l(ltion for a system of
-Ze~
2
Ze' e
E,, = - 4J1'foTi
- - -4'11'foT2
-+- _ .
411'foT12
(4.2) independent particles.

AlOllU with nwny ekclroll'
by b, we must then write
"'.,om = -.( I )"'~(2),
resulting in a probabili~y distribution
It.,o",I' = 1 ",,,(I)'h(2) 1 ~ = 1y,,,(1)1 2 1'h(2)1 2 .
Due to the motion of the elect rons, the average central field that. 0111.' electron
produces 011 the other deviates from the l /r coulomb field produced by the nucleus.
This obviously requires a slight modification of the wave functions ta(l} and ,/1&(2),
which arc no longer identical to the hydrogenlikc wave functions. The change
affects the radial part R~ I but !lot the angular part 1',., of the wave function be-
cause the res ultant force on each electron is still a central force. Using appropriate
mathematical techniquC9, we can optimize the electron wave function, and so ob-
tai n t he energy levels of the atom with relatively good accuracy.
However, even if t he func tions appearing in Eq. (4 .3) are 80 optimized, this ex-
pression fo r the wave function of the atom eallnot be correct. Wave func tion (4.3)
snys that electron I is in slnte a nnd electron 2 is in state b. Bu t. the wnve function
corrosponding to electron 2 in state a and electron I in state b, must represent n
stale of the same ellergy as the wave function of Eq. (4.3) and should describe the
state of the atom just as well as Eq. (4.3). T he fact that the wave fu nctiOllS given
by Eqs. (4.3) and (4..5) correspond to the same energy is called ~:rchan(lfl de(lflneracy.
Now, elec/r()n' are identical and lIdUtingllishable, and the most we can say is
that in the atom one electron is in Slate a and the other is in state b. This requires
that the wave function "'_10m be such that 1"'_1"",1 2 (which gives the probability dis-
tribution of both electrons) be symmetric with respect to the two electrons, in such
a way that both electrons play the same role. Neither the atomic wave function
given by Eq. (4.3) nor the one given by E<I. (4.5) meets this rc<luirement. But we
may obtain an adequn.le atomic wave function (incorporating the fact that the
electrons are indistinguishable) by making appropriate linear combinations of
Eqs. (4.3) and (4.5), which happen to be the functions
The student can see that in both cases the expression 1""1<>,,,1 2 is symmetric with
respect to both electrons. T he information contained in the functions given by
Eqs. (4.3), (4.5), a nd (4.6) is expressed schematically in Fig. 4-2.
~I'lte 1 1 - - - - < 0 > - - - -
2 ,
----<0>---- ----<0>----
, 2
~I"I(' Il-----<O}---- --~O)_- --05---
"' - "'.( l lt~t2) "' - >1-.(2)11'.(1) "" -..,.(1)~.c2) :1: ,1'0(2)""",, )
Figure .....2
p
(4.2
4.2) The htliwn olom 153
We shall henceforth call the wave functions given by <1. (4.6) orbiloi U'(Uoe June-
(4.3)
lio/II, sincc they describe the spatial or orbital behavior of the electrons in an atom,
without any reference to the sl)in. T he two orbital functions of E(I. (4.6) are very
di!Terent in one respect. The orbital wavc function with the plus sign,
(4.4)
(4.7)
i~ symmetric in the two electroHS and remains the same if thc electrons are cx-
changed ; that is, 4'8( 1, 2) = 4'8(2, I). 011 the other hand, Ihe orbital wave ftmc-
tion with the minus sign,
(4.8)
is allti,ymnutric in the two electrons and changes sign if thc electrons are cxchanged j
that is, ..... (1, 2) = - ..... (2, I).
This symmctry behavior is reflected in another important prol>crty: The energy
of the atom associated with "'S cannot be the same as the energy corresponding to
4',1. . We note that if electrons I and 2 arc very close to each other, the two tcrms
(4.5) which make up those functions l11"C almost identical, and therefore 4',1 is very small
or zero. Thus the antisymmctrie wave function 4',1. describes a stale in which the
electrons are never too close and as a rcsult, 011 the average, have a repulsion
energy which is relatively small. On the other hand, the sy mmetric wave function
~s docs not exclude the possibility that the electrons may be very close at certain
times, and hence the average repulsion energy of lhe state described by "'S
is larger
than that of "'A. We are th us faced \Vilh the following fact:
Jleljumlik~ atom, may be ill tll.'O clilferent 8tate" ~dth dilferelll energies
alld atomic orbital lI.'ave JUlie/ions ""S and '" .~, corre'po/tdill(j to the same
let of orbital quantum Irumbe" a ana b auiYlled to the two electrons in
the indepelldr.nt IJarl icie model.
In other words, a two-clectron atom has two sets of stationary statc~ Ilnd energy
levels, one described by symmetric orbilal wave functions and the other by anti-
symmetric orbital wave fun ctions. This !mre[y qun.ntum-mechnnieal e!Tect is a
(4.6) consequence of the fact that electrons are indistinguishable.
T he only exception to the above statement is the case in which the two sets of
orbital quantum numbers of the electrons are idellticalj that is, a = b. Then
~A = ",.( 1)"'.. (2) - "'.(2)~.. (1) "'" O. Therefore, when the two ek'<:lrons have the
sallie set of orbital quantum numbers, ollly the symmetric orbital stale is possible.
So far we have considerc<l only the wave funCtions which describe the space dis-
tribu tion of elcctrons. A complete description of the state of the atom rC<luires
Eilher tha t \\'e take t he spin of electron~ into account. Each electron has a spill of ;.
) electron Tho !jpin of an electron may be oriented either parallel or ulitillUrullel to the spin of
another electron, giving a totailipin of one (8 = I) or zero (8 = 0)." Spin states
ValuCli of the quanlum numbers for the total orbital angular momenlum, total ~pin , or
~heir components are dcsignated by capital letteN. The cor~ponding quanlitiee for
lIldh'idual electrons are designated by IO"'cr-ease letters.

4.2) 155
Alcms with many tlIrOllI (4.2
'"
with S = 0 arc called 6ingltiB because they can be obtained in only one way, as
We obtain the totAl wave function of the atom by combining thc orbital wave
fun ction, givcn by "8 or "A, and the spin wave function, given by "Xs or "XA;
shown in Fig. 4-3. However, whell S = I, the resultant spin vector may have
that is,
three orientations ill space, corresponding to M s = + 1,0, and - I. These states
\lltolal = (orbital wave function) X (spin wavc function).
arc diagrammed in Fig. 4- 3. Therefore spin states with S = I have three spill
wave functions and are called tripletB,
The symmetry of .p to,-,>I obviously depends Oil the symmetry of each of the two
z z z z factors, and since there are two kinds of orbital wave fUlletions and two kinds of
spin wave functions there are four possible combinations among lhcm. Now an
examination of the energy levels of the helium atom reveals that the states described
by symmetric orbital wave functions "8 are always singlets (S = 0) and thus
correspond to antisymmetrie spin wave functions "XA, while the states described
by antisymmetrie orbital wave funetiom~ "A
are always t rilliets (S = 1), and thus
correspond to symmetric spin wave functions "X8. Thus it seems that the only
slates that are allowed in nature are

symmetriC ) ( UntisymmetriC)
.plot&1 = ( orbit~1 wave X spin ~\'ave = "S"XA,
function function
,11 .1 " - I
singlets, (4. 10)
1
S ... O (.inKlct) S .. I (triplet)
antisymnlCtriC) ( symmetriC)
Fig. j.-3. Spin slates for a system of tll'O electrons. "1<>1&1 = ( orbit~l wave X spin ~vave = "A"XS ,
functIon function
triplets. (4. 11 )
It can be shown that the lotal spin wave function of the singlet (8 = 0) state is
QI!Ulymmetrie in the two electrons, while the three total spin wave functions of the In either case "1<><&1 is antisymmetric, since it is the product of a symmetric and an
triplet (8 = J) state are Iymmetric in the two electrons. These spin wave functions antisymmetrie factor. This is a far-reaching conclusion which may be stated in a
may be expressed in tcm18 of the one-cleetron s pin wave functions x introduced general fonn for any number of electrons as follows:
in ScetiOll 3.7 according to
The loial UYlt~ function of Cl 6y81em oj dtc/rOll6 must be ClTlli6ym"ltlric.
x, - ~ [x+(I):C(2) - x+(2)c{1)], Als = 0,
III the I\ext section the implication of this statement regarding many-electron
atoll1s will be ca.refully analyzed. Now we shall briefly discuss the way it affects
r +( I)X+(2)' J1/s = +1, (4.9) the energy levels of the hcliumlike atoms.
x, _ Jz [X+( I )L(2) + x+(2)x_( I )], M 8= O,
Figure 4-4 shows the energy levels of helium when one of the electrons is always
in the ground state Is (orbital quant.um numbers n = 1, l = 0, 111, = 0) and the
L(1)L(2), Ms = - 1. other electron is in the same staw or in an excited state. The orbital quantum
numbers of the excited electron are shown at the top M /l.S, I~p, lid, etc. The energy
values listed arc relative to the ground state. Some of the possiblc transitions arc
The valuc of M 8 = 1/1, 1 + 11Id corresponding to the componcnt S. of the total alllO shown. Atoms with S = 0 constitute paralttlium and atoms with S = 1 con-
spin is given fo r each wave function. The factor 1/..;2 is for normalization pur- stitute orlhohelium. Note that no transitions bctween the singlct and triplet states
poses. Note that the W!lve fUllctions correspond to the situations described in arc indicated. Such transitiolls are quile improbable, since they involve a spin re-
Fig. 4-3. Summarizing, we have arrangement, which is possiblc only if strong spin-dependcnt forces are prcsent.
Thus, ill a SCIlSC, we may N'gard orthohelium and Imrahelium as two different gases.
Singlet state (S = 0): antisymmetric spin wave function XA,
The proportion of atoms of each class is threc to OIlC. Note that state n = 1 exists
Triplet state (S = 1): symmetric spin wave functiona.xs.
 po

156 AlomI wuh many tEte/rolll (4.2 Th~ hdium mom 157
4.2)

i
Slngleu (8 ... 0)
TripLet.8 (8_1) EX/IJlII'I. E 4. J. i"ormalile the wave function8 ~8 and~ .. gh'cn by Eqs. (.. .i ) and (4.S).
oUI lip I Mrtd IIf
lid Nf lip
5<>111 , 1011 ' Let us designate either ~8 or"'.. by~. Then, con!!idering thllllhe integral is
IS II' IF i as 3p 31) SF
10
t8ken oyer the coordinates of both electrons, we h8\'e
20 198,30.5 em-l I 2.J .508eV
L__ ~ __ ~ __ ~ __ ~_~ __ ~_~ __ ~_~\
,
,- ,- ,- ,- , , ,- ,- ,- I~ f dr ~ II h 'f:(I)",:(2) ::i: f: (2)f: (l)H~. ( I )~.(2) ",.(2)f.(1)1 dTI dT2
,-
,-
,- 6-
,- , -
, -
,-
I
I
,- ,- ,- ,-
,- ,- ,-
5- - II f:(I)~.( I) dTl/2 f: (2)f. (2) d'2
, 4
I
I 4
4
+ hf;( I )~.( 1} dTJ 12 f:(2)~.(2) d'2
" I
I
I h~:(I)f.(1) h dTJ f: (2)f.{2) d'2
I
3
3
hf:(l)~.(1) f:(2)~.(2)
dTJ 12 d'2.

1I0wO\'er, siTK"C the pro~r functionsv.-. and f .are orthogonll.l ( remember Eq. (2.4 1), we
,v haye that
" i _ I, 2.

Also, the proper functions are normalized, thll.t is,

" , " f. y,:(i)f .(i) dr; - I.y,:(i)y,.(i) dT; - I,

i _ t,2.

I lienee we lind that fy,y, d, - 2. Thie shows that y,J and fA are not normalized. To
I
I normalire the wave functions, iL is enough to multiply them by the factor 1/'-'2, gh'i ng
I HetiuII'
I 20 I
I 0 y,A (I,2) - v'2,y,.(I)f.(2) - f. (2)f .(I)]
" ----- --
__ ------t-'"
II
(4.12)
This also explain!! the 1/ V2 factor in the spin W8ve functiOTlS given in Eq. (4.9),
Fig . ~. Energy le\"{~I.s of helium, showing some tr&n!!.ilions.
EX AMPLE 4.2. Calculation of the energy of the helium atom u!!ing the normalized
wave functions (4.12).
only when S = 0, because in this state bo~h electrons necessarily have the same
501,,'iOlI: The total hamiltonian operator fOf the helium Mom can be written in the
orbital quantum numbers and hCllce the orbital wave function must be symmetric.
form H _ Hl + H2+ Hl2,where
Each stale of the helium atom is designated by a capitallcttcr S, P, D, F. etc.,
corresponding to a total orbital angular moment um of the atom (which is the sum
of the orbital angular momentum of the t\\'o electrons) equal to 0, I, 2, 3, etc. In H, -
each case illustrated in Fig. 4-4, the total orbital angular momentum is equal to
the orbital angular momentum of the excited electron, since the other electron has arc the hamiltonians for each elect ron in the coulomb field of the nutleus :llld
zero orbital angular momentum . A superscril)t to the left gives the value of 2S + I,
or multiplicity, which is I fo r singlet states and 3 for triplet states.
D ue to the spi n-orbit inlemction, the triplet states consist of threc closely spaced co rre~ pond8 to the interaction between the two eleclronJi. !'\ote that
levels corrcsl>onding to the three !>ossible orientations of the total !Spin relative to
_ 1,2,
the total orbital angular lnomelltum. T his is called a fin.e structure, and is not H,.y,.(i) - 1-;.f.(O and
shown in the figure. S-states obviously do not show any fine structure. In add ition
where f;. and f.'. would be the energy of each electron if its intera<:tiOn with the other is
to the states shown in Fig. 4-4, the re may be many other stationary states, in ~('glec ted. Therefore (HI + H 2)~ _ (/';. + I~'.l f, where ,p rcfefil to either of the norm!l.l-
which both electrons arc excited. However, we shall not discuss them here. lled wave functionsy,8 orv.-.. defined by Eq. (4.12), T huJl we may obtain the energy of

158 A loml wilh many t/edroTl, (4.3
the helium Mom by ulling Eq. (2.50); that is,
E- IoI-Ht/tdr - E. + E.+ J"/HI2y, dr.
A direct calculation, recalling the normalized forms of rfs and !fA given in Eq, (4.12),
yiclrb
where
.od
Therefore
We see therefo re that \l'C obtain two possible energy values corresponding, respectively,
to the symmetric wave fun ction IP!J (positive sign) Ilnd to the antillymmctric wave func-
lion""" (negative sign). Since it can be shown that K is posith"c, the state described by
"'" has IO"'cr energy than that corresponding to.,,;, (the difference bei ng 21( ), in agreement
with our previous intuitive discussion. The quantity C is called the coulomb jrUegroi; it
gives the intt:raction energy of the two electrons, assuming tha t t hey are distribu ted with
electric densities PI - -e!+.O>!2 and P2 _ -elt ,(2)1, I'(!speetively. The quantity K ,
ealted the tJ'chang4J intf'gr(ll, gives the interaction energy of charges "ith densities
This term has 110 dassiea! exp!snll.lion and is a pure quanta! effect, resulting from the
identity of the electrons. The evaluation of C and K is a rather tedious IJI'OCeSS because
the variables arc not scpflrated due to the preS('ncc of thc factor '12.
4 .;1 The "::~clu~;on 'rlnf"lple
T he discussio n of heli um and hcliumlike atoms in the preceding section illustrates
the kind of logic that must be sPI>licd in discussing many-clectron atoms. As a
reasonable starting point, let us agaill use the independent-particle model and con-
sider that Cl\ch electron moves in t he s Urnctive electric field produced by the
nucleus plus an average repulsive electric field due to the other electrons. Thcre-
fo re wc can describe the dynamical stale of each electron by four Quantulll numbers:
71, I, mit snd 111 The first three quantum numbers give the orbital motion and the
fourth the orientation of the spi n. T he energy of the orbital motion depends only
on 11 and I, and thus each electronic stale is identified by the symbol 111. All elec-
trons having the same til quantulll numbers arc called equiva!eut. The complete
state of the atom is specified by indicating the number of equivalent electrons in
Cl\eh ul state. This constiLutcs wlll!.t is called a configuration. If there arc !I': electrons
In somc atoms the@pin-orbiteffectissufficientlystrongtorequire lhe usc of the quantum
num bers II, I, j, and III, instcad. \\,hcn this situation exists, it is called j -j cOllplirll1.
4.3) The ezclwion pl'inciple 159
",,""",--.------,,-----,------,,-----,------,,-----,------,-------,
Xe
, Li
..
' "
lib
0 7U 00
IU
'"
,\Iomic ",,,,,bc . Z
6U
Fig. 4-5. Ionisation cnergy of the elements as a function 01 atomic nu mber.
in the state nl, this is indicated as nl~. For example, the ground-state configuration
of helium is l S2 and the first excited configumtion is Is 25.
The independent-particle model provides an excellent approximation when
combined with another principle, which we shall now explain. It is well known
that chemical elements exhibit certain regularities in thei r physical and chemical
properties. T hese properties repeat themselves in d ifferent clements in a more or
less cyclic form, and successive cycles or periods arc completed at the atomic num-
bers Z = 2, 10, 18, 36, 54, and 86, corresponding to the (so-called) inert gases:
helium, ncon, argon, krypton, xenon, and radon. Ine rt gases arc characterized
chemically by their very weak or almost nonexistent capabil ity for entering illto
combination with other clements. T he periodicity in the properties of the clements
is e)[emplificd in a striking way by the ionization energies, IL!! shown in Fig. 4-5,
whe re we sec a trend which mo re or less repeats itself after eaeh inert gIL!!.
Chemists ill the ninet.centh century noticed this periodicity; in 18W the nussian
scientist Dmitri i'l lendelecv proposed his celebrated periodic classification of the
clements in cycles or periods composed of eight elements eaeh. This cla.ssification,
however, did not work well a nd some elements, such IL!! t he tram:li tion elements and
the rnrc earths, d id not fiL easily into this simplified scheme.
The regularities in the atomic properties suggest certain regularities or periodici-
ties in the motion of the electrons in an atom. To explain these regula rities, the
Swiss physicist Wolfgang Pauli (l900--1!)58) a round 1925 proposed a new rule, since
called the uclUBion pn'lIciple. This principle not only explains the periodic physical
and chemical behavior of the elements in a bea.utiful and simple manner but it also
correlates many other important e)[IJCrimental facts of atomic structure. Using the
inde j:l(mdent-particle model, Paul i's exclusion prineil>le states t.hat
110 to tiee/ron, in an atom may hat>e the same set 01 qualltum JIUlnber,.
 po

160 A/oms with mallY tw/rQtl, 4.4) 161

(4.3

Th is important rule is equivalent to the more general principle introduced in ,t.'t #}"f'f'lronlf" ,fiJilrllf"IIIrf' f,1 , l/un."
Section 4.2 which slated that We shall now consider how we may use Pauli's exclusion principle to dete rmine the
electronic configurations of atoms. Let us first calculate the !lumber of combina-
lht tolai utWt JUI/CIiOIl of a sy8/Cln of eleelrOIlS mU8t be alliisymmelric. tio ns of quantum numbers lit/ and m. that arc possible for each value of the angular
mOlllentum I. This will give I he maximum number of elcctrons that can be accom
This may be considered as nn altemative and more genoml statement of the exclu- modated in t he state Ill. We know tha~ for each va.lue I there are 2l +
I values
sion prineil)1c. A si mple mat hematical consideration reveals that the antisymmctry of 111/, and for each I, /III pair we may have the electron with spin UI) or down
of the wave function implies the validity of the exclusion principle as expressed ill (m. = !). So the mllximUIll /lumber of electronll that can be accommodated in
the first statement. However, the antisymmctry of the total wave function is Ii +
a state nl without violating the exclusion principle is 2(21 1). T his ill indicated
morc genoml statement; it applies (lvcn if the indcpcnd cnt-]mrlic!c model is not a n explicitly in the following table.
adequate 9.PI)roximation."
Angular momentum, I: 0 1 234
We shall next illustrate a simple way of writing 8n antisymmctric fun ction using Symbol: s p d f g
the independent-particle model. Assume an atom with N electron!:!. Le t us desig. Oeeurmtioll number, 2(21 + I): 2 6 10 14 18
nate by Il. single letter (say a) all the orbital and spin quantum numbers 11, I, m/, 111 ..
of a given independent-particle state in the atom. Then a configuration in which T hen, in the building.up process of the atoms from Z = J up to Z = 92 (Ilnd on),
one electron is in state a, anothe r in slate h, alld so on, may be expressed by Q, electrons occupy the lowestlying energy states availllbll', each up to the Illaximum
determinant!!.l wave fun ction number nllowed by the exclusion I>rinciple. Once an nl s ta.te has received its full
quotn of electrons, the next state begins to fill up.
. ,(3) The order in which the successive III
oJ.- ~(3) states fill UJl is indiClltcd in Fig. -1 - 6.
(4.1 3)
There nllly be slight changes for some ToUlI numl.>cr 01
Eledronll el.,..,trons at each
parlicubr atoms, but in general the or in 8M-II .bell completion
der is as sholl'n. We observe in thc first
T his wave fU llction is antisy mmetrie because, if we interchange two electrons (let plnee certuin Uenergy gaps ~; th~t is,
us say I and 2), this is equivalent to interehanging two COIUllll1.S, and then the regions where the energy difTCI"Cnce be-
determi nant changes sign. On the other hand, jf two electrons have the same set tween two states or Ic\'els is Illuch larger
of quant um numbers (say a b), the dctermina nthas t.wo identical rows, and there- tlmn it is between lel'cls below the lowcr
fore is identicaHy !lero. This shows the equivalence of the two state.nlents of the or above the upper. The energy gaps up-
exclusion princi l>]e when the independent.particle model is used. T he l/ ../N! fae. pear betwecn Is lind 2$, between 2p and
tor is for normalization purposes only. 3s, 3]> and 4s, 4p lind 5s, and 80 011. En
As a oonerete example, let us consider the function ~,.x s, where oJ.-iI is given by
ergy levels grouped between two energy
gaps oonstitute a shell." Ench 1!1 state
Eq. (4. 12) and Xs by Eq. (4.9) with M s = 1. Theil 'P~~~~-6} ------36 (Kr)
eompooing a shell is called a lJub8hell. 3d 10 18
4$ - 2
The maximum number of electrons in
~ueccssive c0I11 I>\e1e shells occurs pre
~ ====::~}s
------18 (AT)
cisely at Z = 2, 10, 18, W, 54, and 86,
which arc the inert gnses, as required by ------10 (Ne)
"~(2)X+(2) 1 '
cxperimenl:11 evidence. There may be
-t(2)X+(2)
another inert gas lit Z = 118, but no
ntom with such n high number of elec
,, - -- ,
2 ------2 (lie)
T his is a determi nant of the t,yJ)C of Eq. (4. 13) with N = 2, except that. the orbital trons has been found in nature or yct ..-ig , 4-6. Shcll structure of atomic ('ncrgy
and spin l>arts of the independent-particle wave functions are shown sel>arately. made artificially. levels,

.. The principle of antisymmctry of the total wavc func tion tlPI)lics not only to clectrons .. f-ip,rctroscopisU! aliO IISC the term 3htil lO de~ignatc all states in man y--c\cctron atoms
but also to olhcr fundamental particles, such IL'S protons snd ncutrons. All particles corl"('spollding to lhe same n. In that SCI1!1l', states with n _ 1,2,3,4" .. constitute the
described by anlisymmClrie total WS\'e functions, (or reasons to be cx])lailled in Chapter 13, A, I"~ ,II, .V, ... sh('11s. This is the salllc terminology used in Chapt.cr 3 for onc-<'Icctron
are called /tTmioWi. atoms.
 .,

,..
TABLE .... I Electronic Confi g urat ion or Atom!! 4.4) Ekdroni~ ,uudW"t oj o/onu /63

.~ ,
.
.- /, 0::ilJ /,n-t:o
'. -=:;
,~

,. ,.
o
Z
~

o. 0'

' <
:) ~
-.
z ]
,
J! o .
~
g ~
. '
~~
0'
:~ ~
-." KW- K~
Il

.
0 "

. .
00

,, II '8
,.''" 13.MI5
""... , 'I','s
Te 4d, 0.',at SI >' !}.OI
" , " " "
II, '8 Z.I .~ I ~ 1'3" ~I' 0 601 11 5 p a 10.454
/, !TIITI
,
,.
U '8
'S
[He]
"
,.' 5.300
0.320

".
Xe
C. 's
4!j' o &o f 5p'

[XeJ tit<
12.IV
3.8n3 .rr.rr- rm:ITI rtTlITTI ItITTIIn
~ ~ ~
.
Li
2$1 21> 's &'
" "" C,'" 'G,
. .
f P ltt 8.200 S.210

,,1 0, ,.
C 3" 0 :!s1 2p' 11 .256 t D 3/. 6d &' 5.61
N s
' 1',
2s' 'l~ 14.5-IS
"" 1', . f ~ tie' '.M
" "
21'1/2
201 2 'lp.
:!sf 21>'
13.61 4
17.41 8 60
I'm '"
l\d '" t
41' 6.1'
4f' 6.11
...S
5.51 /,ITIOJIIIJ Ilfl l l l l l
10 Se
:-;.
'S

"'s [/I.""el ....'

:!S' 2p' 2 1.M9
5.138
"" ","m ' Hit.
'Fa
41~ 60'

.e ""
41' 6011 .[ill , J..I.
o

""" A'
63 'S 5.67
Mg 7 644 Cd '", 4f' 5<1 601'
"" 6.16
' 1'111

".
30' 31' 5.964 Tb e ll 1511 4f" 61' 6.74
,.
Si ' 1'0 8. 140 Fig, 4-7. Ground-state electronic configurations of the atoms of thc first ten element8,

""" C, '1'.,.
35' 31" 4fl o (Is'

S
'S
31',1
ls' 31"
301 31"
10.484
10.357
"" '''~ I'
68
Dy
II,
Er '116
4f" Gi'
4f12 61'
6.82
showing how they are built UI).
3.~' 31'~ 13.01

"" ~ "" Tm,.,Vb 's 2FT/' 4f> 3 !}S,

's 30 ' 3po 15.7M 4f" fill' 6.22

.. .
5<1 &'
The electron configuration of the ground state of the atoms of the different chem-
K 's ' "" T.'" 'F, ' Da/t 4( " 6.15

'"" S,C.Ti 'n",

IArI U 39 ical elements is given in Table 4-1.
4f" 6<1' & ' 1.'
'S
3d 4~'
6.111
' .M ,.
., " R, '", 'F:lJI 4f " 5<1' 60I f 1-" It is instructive to see ill morc detail how the first 10 elements are built up.

..,." C, '"'0.'s'F."'S
W 4f" 5<1+ 61' 1."
22 3d" 4s" 41" 5<1' list 1., This is shown in the block diagrams of Fig. 4-7. The lHIubshells have one block
23 V 3d 1 -lsi
3d" 4~
6.14
6.7 64 "" 0. ''S0, 4f" 5<1' 61'
.,
'.1 accommodat.ing two electrons with opposite spins, and the p-subshelis three blocks

" C," 'F.,.

:\In 3d ' h'
3<1 6 "", ,., "" A,"'" 'S'Do
7.432 'FIJ'

I X~,
4f" 5<1' 60'
4f" 5<1' 60'
4f14 MIG[ Go
,.9.22" (m, = + 1, 0, - I ) accommodating six electrons. It must be noted that in filling a
p-subshcll, we have always placed as many electrons with parallel spins as possible.
"'" C.Ni ' F.
3d' 4."
3d 1 4s'
3d' 0 ~I
7.86
'-033
80
81
" T' 's
II,
t pi/ t
&'
60 ' 61'
10.43~
6.106 This is because it is known experimentally that
" C. "
30 lin
'S
3<1 '04.
3d 10 4.' 41'
7.7U
9.391
"" I'bP, S'I',
IIi
&. 61>"
&I' 611
7.416
7.287 Ihe rewlant spill of the ground stQ./.e oj a/oms has Ihe largest p08sible
"" ,R., ''sI',
' I'll. ' .00
",. G.
31
33 Ao
3 /'0
S
3d' 0 4.' 41'"
3d " 4. 1 (1)'
1."
9.81
86
'1'3/'
!}oj' 61"
&' 61'~
(Is' 6p6
8.43

10.746
value compaliblt with Ihe exclusion principle,
'I', 3d 'O 4"~ 41"
" 3d 10 40" 4p"
9.76
,',
..
B, "1'." a result known as lhilld's nUt, T his property can be explained as follows. We
"" K. 'S 11.8 4 S7 's Illnl I,

,.
31 Rb 's [K rj .......
3<1 ,0 4.' 41 >0

.
13.996

..' .m'" "

4. li6
S8 R.
",
'S
" 1)3,.,
,,'
6d 7,"
5. 277 know, from our discussion of lhe helium atom, that the ground state must be that
state in which the repulsion of the electrons is as small as possible, and this requires
Tb
..
6d t 7,2

.
00 ' F,
38

.,"
S,
V
Z,
N"b
..'8',
's
' DJlt

&01 /.
'
. . ..
. ....
4<)' Se'
"'" "
. .81
93
P.
U
,.
1'1'
'1\ 11 '
'
' Lli lt
'.'0
61' 6d 7i1t
Sf. 6d 1st
51' 6d 1s'
... a maximum antisymmetry in the orbital part of the wave function, Since the total
wave function must be antisymmetric, we conclude that the ground state corre-
sponds to the maximum symmetry of the spin wave fun ction, which occurs when
"" 6f07;,'

....
" T,R, O'SF.
;1.1 0 7. 10 Am
<3
Rb 'F,,"
Ss'
. ....
4(1 '
4d 'Se
'-12'
7. 3%
7A61 "" Cm
Rk
"'d. 51' 71'
5(1 6d 7, '
(51' 6d 7,')
the spins of the electrons are as parallel as possible.
Thcre are other interesting aspects that are worth mentioning in connection with

., PdA. 's's
. 4d'0 8. 33
"'"
CI (51" 6d 7 )
(W o 6d 7,')
Fig. 4- 7. For cXftmple, hydrogen has a single l s-electron and lithium a single 2s-

..'" ,.
E
4d l0 .'ie 7.5H electron, but in the lithium atom the 2s-clectron has available the relatively close
' 00 Fm (5f" 6d 7.')
Cd 'S 4d l0 .'ie' 8.991 2p-levels as wcll as having a sma[[cr ionization energy (5.5 eV com pared with 13.6 eV
S.
1'1 /1
'P,
4!j' .'ie'5p
4d'.',a' 51>'
5.785
7.342
'"
'01
103
;>'lv
:-;"
L. for hydrogen). T hese differences account for the distinct metaIJic behavior of
S 4!j 'o 5g' ::'pl
" Sb 8.639 lithillm, lIot exhibited by hydrogen. Similarly, helium and beryllium have com-
plete Is- and 2s-levels, respectively. However, helium is an inert gas, while beryl-
Chemical symbols in brackets indicate the equivalent configurations of the remaining lium is not. This is because one of the 2s-electrons in the beryllium atom can be
eledrons occupying fiUed shells, Configurations in )lAtentheses are uncertain. excited to a nearby 2p-level, resulting in the excited state shown in fig. 4-8, which

J6~ Aloolllili/h mlllly ~1N:lro/lf
. " ,>
J,lIIIII] J,ITIIIII]
J,ITTiTilll
,>
J,
ti l I I I I
K~ K~ K~
Fig. 4-8. E~cit(!d eleclronic configurations of beryllium, boron, cllrbon, flild nitrogt'l\.
correspondli to the valence 2 obserycd in beryllium compounds. T his excitation
requires all energy of abou t 2.7 eV, while in the case of helium the minimum e:l:cita-
lioll energy is about 20 eV. Similarly, in the case of boron, the first excited state
lIlay be obtained by moving a 2s--electroll intQ a 21H!tate, !lS showlI in Fig. 4-8,
which rc<luires an energy of 3.G eV. T his state explains the trivalence of boron.
The situation in the caroon, nitrogen, and oxygen atoms is more complicilted be-
cnuse new e.xcited states can be produced by reorienting the spin and the orbi!..'l.l
angular momenta of the l>-electrons. A l>nrticularly iml)Qrtallt excited f<tflte of
carbon is ShOWl1 in Fig. 4- 8, which accounts for the letrnvalellce of carbon in many
of its compounds.
We may summarize our analysis by saying that the chemical and physical prop-
erties of n chemical element delX!nd on the ground-state electronic configumtioll
as wcll as on thc nearby excited le\'els. For example, what charncterir.cs an incrt
gn.s is that it is composed of complete shells and thll.l, to excite one of its electrons,
a comparntively large encrgy i>:l required, doc to the large energy gal) sepurating
the last complete level frOIll the first unoccupied level. On the othcr hand, J~toms
such as lithium, sodium, potassium, etc.- with Z = 3, II, IU, ...- are cOIllI)Qscd
of closed shclls plus onc electron in the first level above the energy gap. Ro lithiulIl
has a complete Kshell and a 2s-clectron; sodium has complete K and /.I"'shclls and
a 3s-cleclron, and so on. This last electron is bound loosely and determines the
metallic behavior of these elemcnts. Whcn the /lumber of electrons beyond the
last completed shells increllSC9, the situation get9 more and more COml)lex.
LI.5 '~ ~S ('ullpling
The to!..'l1 angular momcntum of an atOll1 is a vcry iml)Qrt3nt property because iL
determines (among other things) the magnetic propertics of the atom, and the
transition probabilities in ra.diative processes. If the atom is isolated, it!! total
angular momentum is constant. We shall designate it by the quantum numuer J
such that
(4.14)
The Z component of J is determined by th o quantum Humber M such that
J, = Mh
with
/11 = J, (J - I),
Valencc lOud chcmicnl binding will be discussed in ChlOl'lcr 5.
pi
, .5) L-S roup/ing 16'
(4.5
T o cach electronic configuration, thcre may correspond severnl possible values of J,
each associated with a different energy of the atom. An important problem of
atomic structure is the determination of the allowed values of J for each configura-
;.;' tion, and the corresponding wavc functions.
One method of making this determination is called the fr.S or RUI$3e1l--Saunder3
COUfJliWI. Using the independent-particle model with wave functions given by
Eq. (4.13), in which each electronic state is characterir.cd by quantum numbcrs
11, I, m" Rnd III., we may firs~ find the total orbital angula r momentum of the atom,
such that ,~ = E; Li and L~ = E ; /",i' If I.. and M L are the quantum numbers
associated with L 'l and L., then
/'" = AI l.h, M 1, = L, (J.I - 1), ... ,
(4. 17)
with !If 1. = Li mli. To a given configurntion there may correspo nd several values
of L, depending on the relative oricntation of the Li's. Similarly, the total spin of
the atom is givcn by 5 = L; Si and S. = Li S,i' If Sand M s arc the quan tum
nu mbcrs associated with S2 and SOl then
S. = ilf sh, Ms = S, (S - 1), ... ,
(4.18)
with AI IS = Li m' i' Again, to a givcn configuration the re may cOrreSI}(lnd several
values of S, depending on the relative orientation of the 5;,s.
Once I~ and S are found, the total angular momentum for the configuration is
givcn by J :: L + S. The po$>ible values of the quantum numbe r J (which depend
on the relative orientation of I , and 5), arc
J = L+S, L +S - I , . .. , II.. - 81.
(4.19)
T hese procedures are illustrated for three electrons in
F ig. 4-9. All L;'s and S/s are supposed to precess around
their resultants L llnd 5, resl>cctively. In tu rn, L and 5
precess around J .
T he stale of an atom i" cha.racterized by a set L, S, J
of quantum numbers. States of a. configuration with the
same I.. and S constitute a tum. Each ternl of a. configura- s-.,
tion has f\ diffe re nt encrgy. The energy of the different
terms of [~ configuration mllst he obtuined by means of
(4. 15)
rnt her elaborate methods, which we sha.lInot explain here.
But it is ensy to recognize that the energy of a configura--
(4. 10) I. ,
lion must depend on the va.lue of L. Each valuc of L
corrcsl)Qnds to a. different relative orientation of the orbital Fi g . 4--9. II'S coupling.

166 Aloms with many eleciro1l8 (1,.5 4.5) L-S coupling 167

angular momenta of the elect rons, and therefore to a different relative orientation One can easily find the ordering of the terms in a configuration of equivalent
of their motions. This must result in a different value for their coulomb or electric electrons by using two empirical rules due to H Ulld : (I) Of an possible terms,
interaction and thus in a differen t. value for the cnergy of the atom. States of a those with the largest multiplicity (largest S) have the lowest energy; of all terms
terlll having the same L- and S-values but. different J-valucs have practically the with the game multiplicity, the one with the lowest energy is that with the largest
same energy and constitute a multiplet. The SI>\itt.illg of an [;-S tcnn according to value of L. (2) The ordering of the multiplet levels of eaeh t.crm will be normal
the values of J is a spin-orbit eITect. Normally S .s
Lj therefore the total number (i.e., lowest J has lowest. energy) when the subshell is less than half full; the order-
of different J -va\ucs associated with an L-S term (called the multiplicity of the ing is inverted if the subshell is more tha n half full. For example, in the np 2 con-
te rm) is 28 + I. figuration the levels in order of increasing energy are 3p, 10, and LS and t he triplet
A term is designated by the symbols S, P, 0 , F, (depending on whether 3p is normal, with J = 0 the lowest. T hese rules are not rigorous and sometimes
I., = 0, 1,2, 3, ... ) with a superscript to the left. which denotes the multiplicity are not followed.
28 +1; that is, a term is listed as 28+L L. Sometimes a subscript to ~hc right, in-
eoulomb
intcracti(m
Sl'in-orbit
interaction
)"'!(nctic-ficld
interaction
dicating the value of J, is added. T he symbol corresponding to the ground state
of each of the elements was indicated in Table 4- l. ;
,, 'S '1lu
;
Let us consider some examples that illustrate how to find the terms of a con- np2 I
figuration. In the configuration (ns)(n's), which is oomposed of two none<luivalcnt -=-~\,
s-electrons, we must have L = 0, since lL = 12 = O. Thespins of the two electrons '" In
\ '---"---
are either parallel or antiparallel, corresponding to S = I or S = 0, respectively.
I n each case J = S. T hus the possible terms of the (ns)(II's) configuration are
the triplet 3S L, and the singlet LS O. As a second example, consider the configuration
\ 31'
\ _ _-'--_~('::
/-'-'>'----"''''''''''
31'1

(np)(n'p) of two nonequivalent p-clectronso Since lL = I and L2 = 1, the possible ',--------=====

values fo r the res ultant orbital angular momentum are L = 0, 1, 2, giving rise to
Energy leve ls of the nl)2_ eon figuration . ',~---- - -
S-, po, and D-states. In each state the spins may be parallel or anti parallel, which
gives S = 1 or o. Thus the possible terms of the (11 p)(1!'p) configuration are LS, T he resultant average magnetic moment of an atom is proportional to J, which
3S, Lp, 31', LD , 3D . means that a substance eomposed of single atoms will be paramagnetic if J 0
and diamagnetic if J = O. I n the presence of an external magnetic field the energy
levels of a state L S J are split into ZJ +
I sublevels, corresponding to the different
possible orientations of the magnetic moment of the atom relat.ive to the magnetic
Config- Config- Terms field , giving rise to a Zeeman effect. Figure 4-10 shows the energy splitting of the
Terms
uration uration collfiguration np2 due to the several cffects we have mentioned.
!u; an illustration of the complexity of excited energy levels of many-electron
's d, d ll
'D
atoms, Fig. 4- 11 shows some of the energy levels of the carbon atom. T he ground
.'
p, pa
'S
'I'
d2, d S
d3, d 7
LS, LO, 10, 3p, 3F
21',20, 2F, 20, 2H , oLI', 4F
configuration of carbon is Is2 2S2 2p2; the ground-state term is 3p, with nearby
excited terms 'D and IS. Successive terms corresponding to the excitation of one
p2, p~ LS, 10,31' d4, d 6 IS, II), IF, la, II, 31', 30, 3F, 30, 3H, ~ D
of t he 2p electrons (giving rise to configurations Is2 2S2 2p 11S, Is2 2S2 2p np, and
p' "S, 21', ~I) (p 2S, 21', 2D, 2F, 20, 211, 21, 41', ~F, ~D, 40 152 2S2 2p nd) are shown in the first three columns. Terms resulting from the
exeitation of olle of the 2s electrons, giving rise to eonfigurat.ions Is2 2s 2p 3 and
When the eleetrons are equivalent, !lO~ all the terms arc possible, due to limita- Is2 2s 2p2 3s, are shown in the l:lSt two columns. T he symbols shown at the top
tions imposed by the exelusion principle. For example, the configuration 11S2 of each column correspond to the state of the iOIl left when the excited electron is
admits only the term IS, as we saw for the case of helium. Looking a~ this example removed. Incidentally, the state ~S of the configuration Is 2 2s 2])3 eorresl}(luds to
from a slightly different point of view, we sec that in the IIS2 configuration, if the t.he situation shown in l;ig. 4-8.
quantum numbers 11, i, 111/, and m. of one electron arc (II, 0, 0, +!), those of the Figure 4-12 shows some energy levels of the oxygen atom. Oxygen's ground
other must be (n, 0, 0, -!), giving i1f s = 0, which requi res that S = 0 or a sin- eonfiguration is Is 2 2S2 2p4; the ground-state term is 3p , with nearby excited terms
glet term. Similarly for the np2 configuration, the only possible terms Arc IS, ID, 1D alld IS of the same configuration. The lcvels shown correspond only to the
And ap. This is shown in Example 4.3. Table 4- 2 gives the terms corrcsl}(lnding excitation of olle of the 2]> eleetrons, resulting in configurations Is2 2S2 2 p3 'IS,
to several configurations of e<iuivalent electrons. Is2 2S2 2 p 3 nl>, etc.
 ..
'168 (4.5
4.5) W IXIUpiing 16.
,., -_.p
z,.~ 21,3 (21')
"$ "I'
(-IOCI,aOO (.'1\1-1) __ - - - - ---.:.:; -- --- IS.5O
"0 '50
- '8
--'P 18
'00 _ _ 11) 21J2p2& - 'p
NIl "P lid
00 ----~ -- - _7(;2'~ _____ L - - - - - - (00,R78 tlll- I)-- II.26:
" '" (-I 3{i.~O ,"fI' - I ) _ ____ _ __
118
~
"I' .d
_ _ ___ ____ _ _

._'0 fi - 1fo.93

~== ~, =
ji- In 5- _ 1:-;
5-= In
5--

" "" 5- . _.-1 1)

J==-\_II' _31'
16
sol-
3
"
~~:; --".
I ii
'al) 28 21'"
-

;
70 ..
'0
'n - -' n 8
""
E 00 ,y
"0 13.61
'!!

"
.
'00

,,,
'" s 10

" ,
, --'n
'" {
0 - -' p
'li' 21,2
,
r i@:_ ,1-11. Energy levcb of the carbon atom.

The large number of available energy levels clearly shows that the spectra of ,
many-clectron atoms are much more complex than the spectra of one-elect.ron
atoms_ Several seledion rules limit the possible transitions. For electric-dipole
transitions the selection rules are the following: "
Ill. = :t:I, AS = 0, 0L-____~_-_"__(~
_'_'~,._)_____________________________"
tJ.J = 0, I (no 0 -> 0), (4.20)
Fig. 4-1 2. Energy levels of th e oxygen atom.
llM = 0, J.

The possibility J = 0 -> J' -> 0 is forbidden by the law of conservation of angular olle unit of angular momentum without violating the conservation of angular
momentum, since it can be shown that a photon has an intrinsic angular momen- momentUIll. Also tJ.M = 0 is not possible with tJ.J = 0, bce..'lUSC in this esse again
tum or spin of one ullit (see Section 9.2). Hence it is im l>ossibic for there to be a the conservation of angular momentum requires a change in the direction of J,
transition J = 0 -> J' = 0 with emiSlliOll (or absorption) of Il l)ho1on carrying which implies a change in J" with a corresponding change in M.
 po

(4.5 4.6) Alonu with QIIt or lwo TIOknu tltclroll$ 171

170 Alonu with many &drolll

T Aut.: ......3 Pouihl e m,lI nd m. Valuu for tho: np2 Co n fig uratio n

~J
ML
- I 0 +1

+2 (I, +)(l , -)
:;;.oz
+1 ( I , -)(0, -)
(1.+)(0, -)
(1, -)(0, +)
( 1. +)(0. +) e" A ot!hell "
"
( 1,+)(-1, -)


0 (I, -)(- 1, -) (0, +)(0, -) (1,+)(- 1,+)
~
(I ,-H- I ,+)

- I (0, -)(- 1, -)
(0,+)(-1, -) (0,+)(- 1,+)
,~
(0, -)(- 1,+>
~
- 2 (- 1, +)(-1, -)
,
0
~

EXAMI" "E " ,J . Analysis of the configuration nll~ "

~

"
5<>lul;o ll: In thi" configuration, corresponding to I - I, the quantum numbers of the
electrons are (n, I, m/, m.) and (n, I, ml, m:). To comply with the e.~c1U.'lion principle, the
'I'
fAlleU
two !!(lIs of quantum numbel'll must be different and therefore must differ either in III, or ,lf ~1Ie1l ,\'~hfo ll

m" or both. The pouible values for ml and III: are + 1, 0, - I, and those of m, and m:,
arc + ! or _ i. To ai mllUfy the notation, the spin values will be de!lignatcd <'3 plua (+)
\(1""10 ,
" '" " 30
or minus (_) Bnd the common (Iuantum numbers n and I (-I) will be omitted . Table 4-3 10 30
present.! the 15 combinations of quantum numbers compatible with the excl usion prin- ,\tomic number
ciple. Each entry gh'e!! a IlQMible combination (ml, mJ and (mt m:). They are arranged Fig. >\-1 4. Binding energy of inner electrons as a function of the alomic number.
according to the common values of M L _ m, + m~ and M " - m, + m:. Each set of
quantum numbers corresponds to a wave funetion of thc type given by Eq. (4.13).
Figure -I- 13(a), in which a method developed by J. C. Slater for analyzing configura. ie 2, and this must correspond \(l L _ 2 or a Dterm. The value M L _ 2 is associated
lions is used, Show8 the number of difl'eren~ wave function! corrCSl>onding lo each value with MJf _ 0 only, and must correspond to S _ 0, making Ul) a 'D-term. This stale
of M Land M 1/. From the table or the figure it may be seen that the largest value of AIL requires five wavc functions with M L _ 2, 1,0, - I, -2, and },tiJ _ O. These wave func-
tions are indicated in Fig. 4-13(b). The remaining ten wave functions are properly grouped
,Il l. M,. ,11/, in Figs. 4-13(c) and (d). Arrangement (c) contains all nine combinations of ML - + 1,
.1/ ,.
0, - I, \\'ith !tf II _ + 1, 0, - I , and therefore corresponds lo a term with L - I and
S _ lor 3p. Fina!!y, in (d) , we have the last wave fun ction, with M L - 0 and ,lis - 0,
which must correspond \(l a term ..... ith L _ 0 and S _ 0 or'S. Thus the only I>ossibie
CD-
,, --cp, CD--
, ,
-CD,
,
terms of the flP~ configuration are'S, ID, and 3p.

,, , .If s MS Ms
,,
.1/.<
,,
2 4.6 Atoms .r,lth One or T.Do 1' alcnee Eleclronll

0-- --0 2 0-- --CD The general theory of atomic structure developed in the previous sections can be
illustrated in a very simple way in the ease of atoms composed of complete shells
plus one or two electrons. The electrons filling the comJllete shells constitute the
core or kernel and the remaining electrons arc called the valence electrons. T he
(,,) (c) f. _ I,S _ 1 (d) /, " 0. S .. O binding energy of the kernel electrons is higher than that of the valence electrons
Slaler method for obtaining the terms of the np1.configuration.
and increases rapidly with the atomic number, as shown in Fig. 4-14. The figure
Fig. >\-13.
 po

172 (4.6
'.6) Alonu with one 01' lIDO ~Iell" tkc/ron6 173
gives the binding energy of 18, 28, 2p, etc., electrons as a function of the atomic
num ber. Hence, the kernel electrons are rather tightly bound and remain prac
tically undisturbed in most of the processes in which the atom participates. It is
I[ yd ~"

~
,
l~tM'
Lithi um
,
WP~I
!'iodi",,,
~~~".h'",_
o ~- ,. ~-;,:,;",:,,--~I.<.......:
the valence electrons that arc mostly responsible for the chemicail>ropcrties of the !l 1 601 (iI, Gd(i1 1 (;dar
- -- 't - - - -- r ~--~-- --
atom; these are the OIlCS that participate in chemical reactions and chemical binding.
It ClUJ be easily ShOWll that a complete shell, filled with its full {Iuota of electrons, -, 5 ~~I5; - 61) 5J 511"-=1;; 61' r..1 51
I I_ .11) 4d 41 I 511 ,1.1 .It
necessarily has L = 0 and S = O. Tn other words a complete shell, and by exten-
sion the kernel, does not contribute either to the orbital angular momentum or to
: 4" I , 58 -41'
- --,.----- - - ---t --- - - _~ ~~

the spin of the atom. Hence the orbital angular momentum and the spin of the - 2
31 , 3,,30:1 ,1 3d
,' ~
atom are both due entirely to the valence electrons. For example, in the case
of one-valence-electron atoms, the spin of the atom is S = ; and all energy levels
,,
1-
3>1
I
,,
I .. a

in which only the valence electron is excited are doublets (2S + 1 = 2). For these , , ,,
atoms L = l, where l is the orbital angular momentum of the valence electron. 1 I 31 '
The simplest single-valence-eleetron atom is lithium (Z = 3), which has an 2" - - r - - ::.:: ---- 1"------ - -~-

outer or valence electron and Z - I = 2 electrons in the kernel. The two kcrnel 21' :
,
electrons occupy the level with 11. = I , having a configuration 182. If the valcnce
elcctron moves in such a way that it does not penetrate the kernel, the effec~
,,,
,,
tive ficld it perceives is that of the +3e charges of the nucleW! and the - 2t charges
of the kernel, resulting in an effective charge of +e. Therefore the motiOll and the
-, ,
energy Icvels of the valence electron would be similar to those found for the hydro- ,, "'
gen atom. This, according to our discussion of the wave functions in Section 3.5,
occurs only approximately whenever the angular momentum i8 large. But for low
-0 ,,,
values of the angular momentum, and especially for the s-states (l = 0) the orbit
,
';"(.
of the valencc electron is penetrating and extends through the kernel, even rcach~ Fig. 4-16. Energy IC\'els of hydrogen, lithium, and ,!odium.
ing very close to the nucleus.
Figure 4-15 shows the radial charge distribution of the lithium kernel, together
with the mdial charge distribution of the valence electron fo r the statcs 2s and 2p. +e when it is far out up to + 3t, when it has penetrated dCi)p into the kernel. The
(The radial charge distribut.ion is proport.ional to r 2 [R(r)]2; see fig. 3-13.) We corresponding energy is intermediate betwCi)n that. of hydrogen (Z = 1) and of
thus see that the valcnce electron in it.<5 motion spends some time within the kernel, Li2+ (Z = 3). Since the penetration depends on Lbc angular momentum, the energy
the penetration being greater for an s-orbit than for a p-orbit. The efTective charge of the vulenee electron also depends on the angular moment.um. The smaller the
which the valence electron feels during its motion in a penetrating orbit goes from angular momentum, the lower (more negative) the energy; i.c., the greater the
penetration. So instead of the level seheme shown in Fig. 3- 8, in which all states
having the same 'I have the same energy irrespective of their angular momentum,
r211r{r)f we have the situation dcpicted in Fig. 4-16, for the one-valencc-electron atoms
lithium and sodium. The energy levcls of hydrogen are also shown for comparison.
Lithi um
We see that the larger thc value of II and of the angular momentum I, the closer
the. energy levels of lithium and sodium are to t.hose of hydrogen, because the
orbits are less penetrating and the effective coulomb field corrcsl>onds to Z = 1.
K
However, the more penetrating orbits have energy levels that nrc quite distinct
from those of hydrogen.
2" The I>ossibie transitions of the valence elcctron arc regulated by the selection
" rules (3.17), resulting in the following spectra! series:

o , Sharp series: li S -+ lI'p,

Principal series: "1> -+ 11'8,
Fig. 4-15. Radial charge distribution of the kcrnel and of the vslence eleetron in the
2s- and 2p-st.ates ill the lithium atom. DifTuse series: tId -+ 1I'p,
Bergmann series: /I f -+ 't'd,
 pi

(4.6 '.6) Afomr with /HIe IN' Itro rol.enu tltdrom 175

, '-0 ,.. ... "I' ltd

"
( I07 ,I22 cm- I ) - - - - - ~ -- - Z#'?'I ---- >'1':'1; 13.79
'00
__ 31' 3 -- '0
' _ _ '0

3--'1'
.
Fig. 4-17. Fine structure of the energy >
levels of the !!Odium atom due to the
~
lIpin-Qrbit in tcraction. 8

o 0
0
' --
_ ''88 , .,-0"
' -- 'I' ~-
8 .. 0 S_ l
,
30
nil lip lid Nf nil "II lid nf
'S Ip '0 If I IS 31' 3D 3F
6G1'.~ __ {;,Wf1L%~% __ lZM<' _1_ft'o/% __ r1L.~ __ ~4f!_ 0 '--'r
9__ ,
s- -
7 ~
= ~ --, , ,--
5
, -- S
8-- - - ,-- , - -
, - - , --
7 - - ; - - , -- ,
(; i> 4 6- - , - - ,
6
o [C-",cc=-=c,~~ ___________________--=o
Fig. 4-19. Energy levels of the beryllium atom.

and 80 on. Due to the spin-orbit interactions. all energy levels shown in Fig. 4-16
(except the s-Jcvcls) are doublets, with a separation proportional to S . L. Thus,
1 for example, the actual energy levels of sodium, in which only the valence electron
30 S is excited, arc as shown in Fig. 4-17.
." In the case of atoms with two valence electrons, the situation is very similar to
that of the helium atom. Tho resultant Sl)in of two electrons can be either 0 or 1,
and the energy levels fall in two groups, singlets (8 = 0) and triplets (8 = I ). The
singlets correspond to the two valence electrons with their spins antiparallel, and
the triplets to the two valcnce electrons with their spins parallel. This is the case
of atoms such as those of beryllium, magnesium, calcium, etc. Figure 4-18 shows
the energy levels of the calcium atom; these correspond to the situatioll in which
(I "
only one valence electron is excited. Since in the ground slale of calcium the
valence electrons have the cOllfiguration 4s 2, the excited states correspond to
Fig. ~18. Energy levclJ of calcium, sho wing some transitions. 4s 111, with 1'1 = 4,5,6, ... The values I'll of the excited electron a rc shown at the
 po

X_Rt1.y,pu/ra 177
4.7)
176 Aloou wilh nlQIly tltt:lrom (/1.7

lop of the figure. Some of the possible transitions are also shown. They must con
fonn to the selection rules (3.17). The two dashed lines a rc transitions from a 4 (.\'..well)
triplet to a singlc ~ state; tiley violate the selection rule tlS = 0, and arc therefore
very weak . J, I~
. or course there is the possibility of (!.xcit.ing both valence electrons and this gives 3 (M-!!hell)
nse to new energy levels, M illustrated in Fig. 4-19 for beryllium, which hM the "
g.round-st.n.tc configuration 18 2 282, The first three columns correspond to excita-
J .1
l~
t ion of,only one valencc ~[~lroll, as in Fig. 4- 18 fo r calcium, and the configumtions
aTC Is 2s 1Il. The rcmamUlg three columns correspond to the case in which one
valence elcctron has been excited to the state 2p and the other to III 80 that the
t: .
OOllllgumllOIlS arc Is 2 2p til. Of COUI';>(!, many more excited states exist.
'
'i
f.-.scm
-;;1:>
-, Z (f..-tdoell)

This analysis of atoms with one and two valence electrons should suffice to dem-
onstrate the many complexities involved in analyzing atomic structure. .,"
K. }.
'1.7 X-Il"y Sp,,tru
So far. we luwe considered only e)[cilations of !.he valence electrons, which result. in
"'
<

what IS usually cal1ed the optical $pectrum. But it is possible to e)[cile the electrons
which fill the completed shdls of the kernel. These e)[citations arc responsible fo r
the charncteristie x-rays emitted or absorbed by atoms.
Figure 1- 14 gave the intensity distribution as a function of the wavelength for
the bremsstrnhl~ng from the anticathode in an )[-ray tube madc of molybdenum,
for severn.l appl.led volt.ages. When the voltage is inercnscd, certain vcry shaq>
peaks of mtenSlty of x-rays arc observed, correspond ing to well-defined wave-
lengths. In Fig. 1- \4 the peaks first appear whcn the applied voltage is 25 kY.
(The actual excitation voltage is 20.1 kY.) These peaks arc called ch aracleri&tic
x-rays. The wavelengths of the peaks arc independent of the applied voltage but
depend on the material of the cathode. ' or a 2p electron. I n the first case the configuration of the electrollS that remain
Chara.cteristic x-rays hav.e a simple explanation. When thc electrons in the ;c-ray
tube stnkc the target, theIr energy may be sufficicnt to knock one of the elce-
troms out of the kernel. SUPl>OSC the ejected electron is in the K-shell. When a
K-dectron is removed, an empty state (or hole) is left in the K-shell. Another
electron in a highcr energy level of the kernel (or perhaps a valence electron, or
even a free electron) may fall into the vacant state in the K-shell. Since the amount
of energy involved is fairly lllrgc, the radiation emitt-ed by the electron falling into
Lhe vacant state lies in the x-ray rcgion of the spectrum. The electron falling into
lhe vacant slate of the K-shell may proceed from the D, 101, N, etc., shells and
thcrcf.or~ we have a series of x-ray lincs designated K", K{J, K y , etc. If the vacant.
state IS Ul the [...-shell, the electrons may fall from the M, N, etc., shells giving rise
to the L", I"fl, etc., x-ray lines, and so 011. The x-ray transitions in an atom with
Z ..... 36 a~e illustrated ~helllalically in Fig. 4-20. Note that. x-ray emission is possi-
ble only If a vacancy IS produced in an inner shell, since the e)[chlsion principle
prevent.s a transition from a higher lcvel into a lower, 1>\lt fully occupied shell.
The vacant space in an inner shell may also be produced by absorption of' radia-
tion, resulting in a photoelectric effect for electrons of the K , I.., M , etc., shell!!.
Fig. 4--20. X_ray trll.l1sitions in an Fig. 4--21. Fillc Mructure of xray Iran-
Iltom with an atomic number Z -- 36. I!.ilions.
Actually, ;c-rny transitions are more complex than one would gathcr from
Fig. 4-20, because the encrgy relcased dellCnds on the initial and final terms.
For e;cample, when a Is electron is removed from the K-shell, the energy of the
ion produced is unique. But if the electron is from a full 1..-shell, it may be a 2s
in the shell is 2s2 p6, corresponding to a state ~S112' but in the sc<:Ond case the
configuration of the electrons that remain in the shell is 2s 21>~, corresponding to
2
the statcs 2Pl 12 or 2P3t 2' Therefore there arc three possible states of the whell
minus one electron, each with a different energy. For the M -shell minus one elec-
tron there arc five possible stales, and so 011. These statcs and some of the result-
ing )[-ray transitions arc shown in Fig. 4-21. Thus K " and K fJ lines arc doublets,
the L" line is composed of eight close lines, and 80 on.
T his fine structure of thc energy levels is also renectcd in the coefficient of linear
abso rpt.ion for the photoelectric effect. In Fig. 4- 22 we can sec that a dcfinite
minimum cnergy EK is rcq\lircd to ionize an atom by ");tmcting a K-clcctron.
But if an L-clectrOIl is removed, thcre may be three l"JOssible iOlli7.ation energies
ELI, ELI I, E I. III, depending on the Slate in which thc shell has been left. Similarly,
there are five ionization energies if the electron proeCCf.l from the M-she]!, and so
Oil. This means that when electromagnetic radialion fall s on a material, the
linear absorption cod!icient or macroscopic cross section 2: for t.he photoelectric
effect (Section 1.9) varies as a function of the energy of the radiation, as shown in
 po

178 A/om: wilh mOlty tletlrO/l.' (4.7

Probkn1$ 179

R e f er e n cell

I. "Spectra Inform Us About Atonia, ~ W. Meggers, TM PIt~. Teachtr 2, 303 ( 1964)

";JI 2. " Basic Concepts of Self-Coru.istent Field Theory," S. minder, .'Im. J. Phy" 33, 431
( 1965)
/. IIl:.o!o t l'tion 3. "Terms Obtained from Con6gUnliioIlll of Equi\'alent Electrons, E. Tuttle, 11m. J.
"''''
{,
.\/
,V"
III
II

HI;
,
PltlJ" 35, 26 ( 1967)
4. "Physical B8!lis for Hund's Rule, N. Karayianis, . Im. J. Phil', 32, 216 ( 1964) and
33, 201 (1965)
5. "H . G. J. Moseley," L. Rodman, The PAlJ~. Ttcu:her 3,151 (1005)
HI.! /'hu 6. "The Scientific Career of Charle!! Barkla," R. Stephenson, Am. J. PltlJ" 35, 140
Hwt (1967)
7..4/omic Spectra and Atomic Structure, G. Herzberg. New York: Dover, 1955, Chapters
I and 2
8. Atomic Spec/ro, R. Johnson. New York: John Wiley, 1950
/, { IIIi' 9. TAt Behauior of Elec/rOM in A/orn e, R. lIochstr8!lllCr. N~w York: Benjamin, 1965
Fig. 4-23. Variation of the linear 10. Elemerns of Wove Mechanic." N. Mott. Cambridge, England: Cambridge University
absorption coefficient for )(- and PreS5, 1962, Chapter 5, SectioIlll 2.2, 2.3, 4.5, and 4.6
'Y-rays as a function of the photon
energy. II. Struct ur~ of Motler, W. Finkelnburg. New York: Academic PreM, 1964, Chapter 3,
Sections 8 and 11- 17
12. Quarnum Thfi1Ty of MolUT, J. Slater. New York: McGraw- Hi!!, 1951, Chapters 6 and 7
Fig. 4-22. Transitions rellulting 13. A. Source Book in Phy~', W. Magic. Cambridge, MaM.: Harvard University Press,
~'-;I ~
,
I~
IIcII1o,",,1I
from the absorption of x-rays;
Ihis absorption is accompanied
1963, page 600 (Roentgen)
14. Atomic Spectra, W. Hindmarsh. New York: Pergamon Pre!l3, 1967
c1".trml by electron emission.
15. Principle., of Modern Phym., R. Leight.on. New York: McGray,'-HiU, 1959, Chapters
7 and 8
Fig. 4-23. There is a general trend in which 1.: decreases as the photon energy in-
creases or the wavelength decreases. When the photon energy falls above the
minimum value required to extract an L-.:!lcetron, a sudden increase ill the value
of ~ OCC UI'lJ, since there arc now more electrons with which the photons may interact; 4.1 The energy levela of heliumlike aloma, 4.2 Write, in determinantal form , the
only in this case there arc thrcc closely spaced peaks, corresponding to Bu. ELlIl when one electron is in the ground state three wave fun ctions lJ-tiXA of Eq. (4.10).
and thlll. respceliv(!ly. When the ]>hotoll energy falls above the value EK, there (n _ I) and the other in an excited state NoLC that the wave function for /If., ~ 0
is another sharp increase in the value of:t because the photons havc enough energy (n > I), could be expressed by oonsiats of two determinants.
to eject fl K -c.lectron. These sudden changes in :!: a rc called OO$orIJ(jon edyu. The 4.3 The ground state of lithium has the
K-absorption edge for lead was also illustmted in fig. 1-19. Note that, in geneml, electron configuration \s228. Write out
the energies (or wavelcngtlu~) illvolvcd in x-my emission and absorption arc not the wave function in determinantal form
exactly the same because the ene rgy levels involved arc diffc rcnt. Both x-my Thie ex])rel'lSion a88ume;s that the electron for the state when /lf 1J - 1.
absorption and x-ray emii:ll:\ion arc very useful tools with which to gather informa- in the ground state fully screens one nu- 4.4 -,"' or the ,,2 configuration (sec
tion about the inner shells in an alom. clear charge. Discuss the plausibility of Table 4- 2), write the determin8.ntA.i wave
I n somc C9J;eS the photon emitted in an x-ray transition is absorbed by anot her this e)(preS5ion. Compute the energy functions corresponding to /If 1., - 2,
electron of the same atom, which is thcrefore ejected as a result of all internal levels for helium when n _ 2, 3, and 4, /lf1J - 0 and ilf /. - 1, illlI - l.
photoelectric effect. This process of internal conversion of x-rays into photo- and OO mpare with the experimental result. 4.5 Conaider 8. tllrl:!c-clcctron system in
Why does the accuracy of the above ex- an 8p2 oonfiguration in the ollc-cleetron
electrons is ealled the A W)er effect.
pression for E increase when n increasea? approximation. Write lhe Wlal ,,'ave rune-

180 Afolm wifh rncmy eltcll'Ol!'
tion in delerm inantal form $0 that the
wave function corresponds to M I. - I and
Ms - !.
4.6 Oivcn that thc clectron configuration
of an (!.lorn is 'Is -Ip 3d, write all possiblc
wave functiOIl3 ..... hich corrcsll'ond to M /. -
I and .lIs - i. UIIC the determ inanta l
form.
-1.7 Find the ground-state configuration
foOr the following atom a: (a) Si; (b) !'oln;
(c) Rb; (d) Ni. Also write their ground-
state term.
4.8 Detcrmine the ground-atate configura-
tion and the number of unpaired electrons
in the following atom!!: (a) S. (b) Ca,
(c) Fe, (d) Br.
4.9 (a) Show, on a diagram 8imilar to
Fig. 4- 7, thc occupied stu.tcs for the u.toms
of Si, Cl, and A8 whcn they nre in their
ground-ktate configuration. (b) Write
the electron configuration and the ground
terms of each.
4.10 Calculatfl the angle between the
tatal u.nd orbital angular momentum for
the 4 D3/ 2 state.
4.11 Jolnd the terms for the following con-
figurations and indicate in each ca5C which
term has the lowest energy: (a) lU, (b) n11 3 ,
(c) (ftp 2)(n's), (d) ftl's, (e) (ftd 2 )(n'p),
(I) (ndHn'd).
4.12 List all the po8I!ible radiath'e tT&lllli-
tions for oxygen (see Fig. 4-12) ..... hen the
excited configuration is 2!i 2 21,3 (2 D) 3d
eO).
4.13 Look at Figs. 4-11 and 4-12. Ora .....
some of the l\O&'!iblc transit ions compatible
wilh the selection rules. Oetennine the
wave numbel'll of thcse transitioOns and
check with experimental valuC8, whi ch
may be found, for exa mple, in the lIand-
book oj Chtm~tr1J and Phyt ici.
4.14 Calculate the terms for np3 con-
figuration.
4.15 Give the So, I.. , and J-valuea for the
terms '50, 2S1/2, '1'/, 31'2, 3F4 , 601 , ID2,
and 6Fg/2 .
4.16 Find the tflrms correspond ing to the
configuration nd 2 Apply your rC8ul~ to
determine the ground and fil'llt e.leited
IIlate of titanium.
4.17 Sho,,' that a complete nl shell mUllt
necessarily have L - S - O.
4.1 8 Two equivalent ]!-electrons have
strong spin-orbit coupling. Find the p0s-
sible valuC8 of the l'C!!ultant angular
momentum J if the problem is considered
as j-j coupled. Repeat the problem, con-
sidering L-S coupling. Doea the same
value of J appear the same number of
Umes in each case?
4.19 In DS coupling, one can obtain the
magnetic moment of an atom all M -
-(e/2m.)fJ ) , where } refera to the total
angular momentum of the atom and fJ is
given by Eq. (3.40), with l, 3, and j re-
placed by L, S, and J. Find fJ for calcium
and aluminum. DiseuSli the splitting of a
31' term under the action of a weak mag-
netic field. Find the splitting if the mag-
netic field is stro ng.
4.20 OiscUll8 the 7..ceman effect under ..... eak
and strong magnetic fielda for the transi-
tions 3F -+ 3D and IF ..... 10 in calcium.
4.21 The 4 ID2 ..... 4 11' 1 lrallllition in cal-
cium yields a single line at 6439 A. Wha~
"'a\'elengths are obllCned if cadmium is
placed in a magnetic field of lAO T1
4.22 The relati ve SCl)llration between the
different levels of an L S J multiplet due
to the spin-arbit inte ra ction can be con-
sidered as proporti onal to S . L. Apply thc
relation to the 3F and 30 multiplets. Draw
the energy levels of each multiplet and in-
dicate, by arrows, the allowed 3F ..... 3D
transitions.
4.23 Repeat the preceding problem for
the case of 4D ...... 1' and 41' -> 4S tran-
sitions.
4.24 Using the values give n in Jo'ig. 4- 17 ,
calculate the wal'elength separation of the
sodium D-lines. From the result, estimate
the constant a in Es/. _ as . L for the
3 2 1' states.
4.25 Analyze the 3 20 ..... 3 21' transi tion
in sodium. Determine the ..... avelength
separation, if any, for !hill transition.
4.26 Computfl the energy, in electron
"01111, of ~ red (6500 A) and of "blue-
(4000 A) photonll. Using the energy seale
on Fig. 4-18, delennine whi ch of the llin
glet and triplet transitions for calcium are
in the "isible range of the spectrum. Com-
pare your rough estimates with a table of
wavelengths.
4.27 An expression which fits the energy
levelll of the valence electron for one-
valence-clectron atoms is
E~ - - Rhc(Z ~ S)2/(n - W,
atomic number. ) From your plot, verify
where S is the screening constant and 6 is
the quantum defect (which depends on the
n and I values of the particnhH valence
electron). Values of 6 for lithium and
~odium are:
d and silver. Com]IIlTe the energy values
Li (Z _ 3) 0.40 "
0.04 0.00
Na (Z _ II ) 1.37 0.88 om
For S, one takes a value equal to the nu m-
ber of electrons in the kernel. Find the
energy of the ground state and the firs~
b 'o excited statC8 of the valence elec-
tron in lithium and sodium. [Hint: See
Fig....... 16.]
4.28 The transition from the 31~le\'el to
tbe 3s-level of sodium l'C!!ults in a line with
a wavelength of 5890 A. (We ignore tbe
double' structure.) Compute the wave-
length, using the \'alues of the energy levels
given by the exwession in Problem 4.27,
and compare with the experimental value.
Repeat for the 2p ....... 2s transition in
lithium.
<1 .29 From the information contained in
Fig. 4- 14, estimate the energy of the K-
and L-nbsorption edges for aluminum and
oxygen. Plot tbe x-ray absorption curve
for these two substullt"Cs in that region.
Prob[mu 181
4.30 The following K.-lines have been
measured;
magnCllium: 9.87 A; sulfur: 5.36 A;
calciull1 : 3.35 A; chromi um: 2.29 A;
cobalt: l.i9 A; coPllOr: 1.54 A;
rubidium: 0.93 A; tungsten: 0.21 A.
I'lot the flqua re root of the K ..-frequency
agains~ the atomic number of the element.
A young graduate student of Ernea~
Rutherford 's, by the name of H. G. Mose-
ley fou nd, in H112, an empirical relation-
shil) of thc form ";; - A(Z - e). (This
relation llCTIed 10 clarify the concept of
this relatiou and estimate the values of A
and c. Develop an cX]llanation for this
relation of Moseley 's.
4.3 1 Calculate the wavelengths and euer-
gies for the K", x-rll}' lines of aluminum,
pot.ll.Sllium, iron, ni ckel, t in e, molybdenum,
with thoae shown in Fig ....... 14. UllC the
M()I!eley function of the previoU!! problem.
4.32 The Ka-line for cobalt is 1.785 A.
Wh a t i8 the enerKY difference between the
h and 21H1rbitals in cobalt? Compare
with the energy difference between the 18-
and 2p--orbilals in hydrogen (i.e., the first
Lyman tiue). Why is the difference much
larger for cobalt tha n for hydrogen?
4.33 (a) The K-absoqltion edge for tung-
Slen is 0.178 Aand the average wavelengths
of the K-scriC8 lines are K" _ 0.210 A,
K, _ 0. 18<1 A, and K., _ 0.179.t Con-
struct the x-ray energy Icvel diagram for
tungsten similar to that in l~ig. 4-20.
(b) Wha~ minimum cnergy is needed to
excite the l.rllCr[es for tungsten? Det.cr-
mine the wavelength of the La-line.
4.3<1 The " I-fLbsorption edge in tungstfln
is 1.02 It I\ ssunle that a K,,-photan is
absorbed by one of the 2s-eleclrons in an
:\ugcr process. Determiue the velocity of
the ejected photoelectron.
 po
5 5.2)
MOLECULES
5.1 Introduction
5.2 The Hydrogen Molecule Ion
5.3 Molecular Orbitals of Diatomic Molecules
5.4 Electronic Configuration of Some Dialomic Molecules
5.5 Polyalomic Molecules
5.6 Conjugated Molecules
5.7 Molecular Rotations
5.8 Molecular Vibrations
5.9 Electronic Transitions in Molec ules
5.10 Conclusion
TM hydrogen mol~cuu: ion 183
5 . 1 I ntrod llction
An important problem related to t he structure of matter is the st.ructure of mol-
ecules. Why do carbon atoms combine with four hydrogen atoms, formi ng meth-
ane, but never with t hree or five hydrogen atoms? Why is the CO 2 molecule linear,
while H 2 0 is bent and N H3 is a pyramid? Why does benzene (C6H a) have the
form of a hexagon with aB hydrogen atoms in the plane? How call hydrogen atoms
join together to form the molecule H 2 but. never form H 3? Why are the spectra of
molecules so complex when compared with atomic spectra, ranging from the micro-
wave up to t he ultraviolet? These and many other q uestions eQuId not be answered
satisfactorily before the quantum t heory was develol>ed. One of the most spec-
tacular successes of the quantum theory is the answcrs it provides to many of the
questioll8 physicists and chemist.':! have been aski ng abou t molecular structure.
We cannot say, however, that our view of molecular structure is a closed chapter
of physics.
Let us begin our study of molecules by asking ourselves: What is a molecule?
The first impulse is to say that a molecule is a group of atoms bound together by
some kind of interaction. But this immediately raises new questions. Do the atoms
conserve their individuality? How is t he motion of the electrons affected whcn a
molecule is formed? What kind of interaction gives rise to a molecule? We may
also adop t an opposite view by saying that a molecule is a group of nuclei sur-
rounded by electrons in such a WilY that a stable arrangement is produced. This is
the natural extcnsion of the concept of an atom, whieh is a nucleus surrounded by
electrons. Then instead of looking at the H 2 molecule as two hydrogen atoms, we
may consider it as two protons and two electrons arranged according to the laws
of quantum mechanics and held together by electromagnetic forces. From a struc-
tural point of view this second approach is more fundamental than the first.
However, as it is in many cases, an intermediate position is t he most eonvenient.
When two atoms combine to form a molecule, the more tightly bound, or inner,
electrons of each atom (which fill the complete shells of their respective kernels)
arc practically undisturbed, remaining attached to their original nuclei. Only the
outermost, or valence, electrons in the unfilled shells are affected and they move
under t he resultant forces of the ions, composed of the nuclei and kernels, as well
as their mutual repulsion. These valence electrons are resl)()I\sible for chemical
binding and for most physical propert.ies of the molecule. This int.ermediate posi-
tiOn is t.he model we shall adopt ill this chapter ; it is an excellent approximation
for analyzing molecular structure.
iJ.2 The lIydrog@n !t~o'ec,tle Ion
T he simplest of all molecules is the hydrogen molecule ion Ht. consisting of
two protons and one electron. Chemists write the fo rmation of this molecule as
+
B H + ...... H t, whe re H+ is just flo proton. Til other words, the Ht moleeule is
formed when a hydrogcn atom captures a proton. But once the Ht moleeule is
formed , it is no longcr possible to tell which is the hydrogen atom and which is the
 ... ,

(5.2
'" -.
5.2) TM hydrogm moit/:/l/e ion "5
,., To discu$IJ the stationary states of the Ht molccule, we first assume that the

r /
,
, ---- ,,,
,
\'2
two protons lLTe at relative rest, and set up SchrOdinger's C<juntion with a potential
energy

" -- ,
()C,_______, ___ ____,,()
(5. 1)

Fig. 5-1. The lit molecule ion. I'L 112 T he first two terms in the I)arcntheses give the attractive polelltial energy between
the electron and the two protons, and the third term is the repulsive potential
proton. Our picture of this molecule is that shown ill Fig. 5-1: an electron moving ellergy between the two protons. The variation of the electronic potential ellergy
in the electric field of two protons which arc separated a distance T. along the line joining lhe two protons is shown in Fig. 5-3. It resembles the double
We might say t hat the electron docs not remember which proton it initially be- potential well considered in Section 2.8 in connection with the KH3 molecule.
longed to. T his lack of memory is clearly revealed by chargHXchange collisilm8.
Suppose that the electron is initially fUI8O<:iated with proton PI, and proton P2
approaches the hydrogen atom from the right from a large distance (Fig. 5-2) .
In the region of closest approach the H t molecule lasts Dilly a short time and then
,, ,,
,, ,,
breaks apart. When this happens there is a certain probability that the incoming
proton will take the electron with it. T hus we may write the process r..s

H+ + H --t H t
?

"- H
H+ + H

+ H+
(elastic collision),

(cbarglHlxchange collision).
,,' ;I!'. 5-3. Potential energy along
the line joining the two nuclei in
lit and 112.
in:
I
,
,,, ,,
,
,,
The solution of Schr(klingcr's c<!uation for Ht, whic h is ralher COml)lex, will be
The Telat ive probability of the two processes shown above can be calculat.cd tI.'S a sketehc<1 in Example 5.2. A~ the moment, however, we shftll follow a more intuitive
fUllction of the energy of the incoming proton. The result checks well willi experi- reasoning. First we shall consider the situation in which the electron is initially
mental evidence. orbiting around proton p" forming a hydroge.n atom in its ground state is, and
the proton P2 (or H +) is at the right, very far away. The wave functioll of the
II elect ron is practically undis turbed by proton P2. Thus it coincides with the hydro-
1'1 e gcn Is-function drawn in Fig. 3- 9. Thcrefore, if we dmw the electron's wave func-

-------
'"
------------>0--
--,,------------ lion along the line joining the two protol\e!\!J a function of the distance from 1)1,
we obtain the curve shown in Fig. 5-4(n.), which shows that the clectron is to be

(0)
'"
(b)
found predominantly around proton PI ' Suppose now that the electron is ini-
tially orbiting around prolon P2, fomling a. hydrogen atom in the ls-state, and
II t hat proton 1)1 is far to the left. Then the wave function of the electron is IlSl!hown

"'''' ... ,
, .r" 11 + ... __ '"
-'
/ in Fig. 5-4(b) .
As the separation between the two protons decreases, the wave function of the
electron is disturbed because the approaching proton ( P2 in Fig. 5-1 (0.) and PI in
-------- ------Pl
_ - - ... - PI
--------- ---- -------- Fig. 5-4 (b trics to pull the electron away from the other prolon. The symmetry
of the electron's potential energy shown in Fig. 5-3 suggcsts that the probability
_... ------ distribution of the electron must exhibit the snme symmetry. T hus, once the lit
molecule is formed, the electron wave function must have l)rOnOUnccO peaks around
each proton, where the potcntial energy is less, according to Fig. 5- 3. The two
(.) (d) possible wn.ve functions for !-I t which have the required symmetry for their I)rob-
ability dis tribution are shown in Fig. 5-4(e) and 5-4(d). The wave function in
Fig. 5-2. Collision of a hydrogen atom (H) and a proton( 11 +), as seen in thec~1 frame (c) is even and in (d) it is odd relative to the center, 0 , of the molecule. These
of reference. (c) Elastic collision. (d) Charge-exchange collision. "'odd,
wave fun ctions will be dc~ig nnted!\!J "'.v~n Ilnd respectively. We ean express
 p

186 Molulu (5.2 5.2) The hyllrogm l1WUtu~ iOll 187

~ &~
W , ,
(0) " (.)
,, , '
'" '"
"'
,
". "

~
Ib) "

I,)
'"
II;
'" (b)

~
p~
'" 0

IIi I "",,~I " #I-h

I,)
(d) ,., 0
'" I~

Fig. 5-5. Probability density for even and odd moleculnr orbitals in Hi'. (Il) Dis-
tribution along the lines joining the protons; (b) lind (c) distribution in a plane containing
Fig. s-t. Even and odd molecular orbitsls in at. the two protons.

eilher wnve fun ction in fUi :\pproximalc way by linearly oombining the hydrogen
wave functions (or a/omic ormtal8) -Ji, and "'2
corresponding to an electron orbiting
around either proton, dc~ignated by I and 2. Thus
(5.2)
"tI-odd .. >/11 - '/12.
These wave functi ons nrc called molecular Qrbitals, abbreviated 1\-1 0. The t heory
we are developing for writing the mo\ceu1:lr orbitals is cnlled the linear C(}1/lbinaliOlI
of atomic orbitals, abbreviated LCAO.
T he stntes corrcs]>onding to molecular orbitals 1/-.v." and fodd of Fig. 5-4 nrc
designntoo, for reasons to be given later, n.s uQ Is and 0' ~ Is. These states must have
different energies, as we can see from the following eX I)!tmntion. Both wave fun e--
tions give maximum probability for finding the electron Ilcar either proton, but.
oI-n-en has an appreciable value in the region between the protons, while oI-odd is very
small (or zero) in that. region, as depicted in Fig. 5-5. Figure 5-5(a) shows the
variation of the probability density of the electron along the line joining the ~wo
protons; Fig. 5-5(b) shows the contour lines of equal probability on a plnne passing
through the t.wo protons, and ill Fig. 5-5(c) the shading indicates the relative
probabilit.y of finding the electron at different places.
When the electron is in the region bet.ween the two protons, it pulls the protons
together, ofTsetting t.heir electric repulsion. When the electron is on either side, it
helps to separate the two protons. In other words, when the electroll is in the
region between the protons, it nets as a "ccmcnt.~ holding them and results in a
stable configuration. In tcrms of energy, we may sny that the state (1,IS cor-
responding to oI-even has a lower energy than (1 .. ls corresponding to ~odd. Note the
similarity between our discussion of the wave functions of Ht and our discussion
of the double potentin.l well in Example 2.7.
The differencc in energy between states (1,15 and (1 ~ Is depends on the sepamtion
of the two protons. Suppose we start with 1\ hydrogen atom and a proton H + far
apart. As the distance between them dccre!l.SC!:I, we get two difTerent energies for
each distance: one corresponding to state 0',15 or wave functi on y..~v~n und n.nother
to slate (1 .. ls or wave function "'odd. Since the negative attractive potential energy
of the electron dominates the positive repulsive potential energy of the Ilroton in
state O', ls, the net energy decreases as r decreases. The rel'erse occurs for O'"ls
and the net energy increases when r decreases. However, for distances smaller
thun a certain vulue '0, the protons are SO close that even in state 0', Is their repul-
sive potential energy begins to dominate the attractive potential energy of the
electron. Thus for dislances 1CS8 than TO the energy corresponding to oI-~ increases
II.'! T decreases. The two resulting energy curves are shown in Fig. 5-6.
We immediately recogni:lle that the ellergy curve forO',ls or ~~""Q has a minimum
at '0, corresponding to the C<luilibrium separation of the two protons, which makes
a stable configuration for H t possible. But the energy curve for 0' .. Is or Y,odd has no
minimum ; thus no stable configuration (or molecule) results. Therefore we may
say that oI-~yft> is a lxmdillg watre junctioll, while ~odd is an Qlui/x:mding to<We junc/ion.
Antibonding wave functions alld states are designated by an !\Sterisk and thus we
write 0':19. The equilibrium proton separation for the l i t ion in the bonding
O"a ls state is 1.06 X 10- 10 In , and the energy of this state at the minimum is
- 2.648 eV relative to the system H (ground state) + H+ at infinite separation. At
the same separation the energy of the antibonding 0':18 state is about + 10.2 cV
relative to t he same reference state.
The states of the Ht molecule we have discussed correspond to the case in which
the hydrogell atom was initially in its ground state. But there are other curves
similar to those of Fig. 5-0 which correspond to excited electronic states of the
 po

188 (5.2 5.2) 189

ZO.[ keY
0.;8 kc\'

8
Fig. 5-6. Electronic polentinl energy
6
11.8 !I. [unction of the internucleflr dis-
> ~:h
tance in Ht for IT, ] ! and .,.: 15 states.
.,-

2 LI [ Itc\'
TO-LOGA
0 o 7.69 kcV 2.39 keY

-2 .," OL-~~-"'I~OO,.-L-L-Lao.k~"-"-~
H~il'l'OnIl
..
vtlodty. unib of 1O~8 ",-I _
-2.&48 eV
Fig. 5-8. Elcx: t ron capture probability in chargc-exchal)ge collisions 48 tl function of
the reciprocal of the velocity of the incident proton.

12 10 microns of mercury or less). The scattered protons are observed at a fixed anglc. In
the process of seattering, IIOme of the inooming prot()ns capturc the electron from the
10 ....
... 2p
hydrogen aloms. It hI!.!! been found [hu the probability of electron capture by the in-
coming protons \'sries with the energy of the prowns, showing pron()unCCtI maxima at
certain proton energies. Figure 5-8 shows the data ()blsined by Lockwood and Everhart,
8 in which the probability of electron capture is plotted against the recip rocal of the proton
"2p
veiocity. The maximum probabilities occur at the energies shown. The interesting featur'C
> is that the maxima are equally Sl'mcOO in terms of l /~.
6
:.::- The quantum-mechanical explanatiOn is very simple. I nitially, when the prot()n is
4 ve ry far from the hydrogen atom, the wave function of the electron i.'! very similar to "'I
~:h in Fig. 5-4. That is,
2 _,IS

O~+-~2'---'!---~6;;"t8---!IO~--~12'--'I~.---f.16'--'I~S---20~---'/~ As the Ilroton aPI)roaches the hydrob'Cn Ilt()m, the wave function beoomes timc-dependCllt.
According to Eq. (2.29), the timc-dependent wave function may be written h
-2

Fig. 5-7. Electron potential energies in Ht for the ground elate and wme excited
stales.
"'here IlE .. f."' - E is the difference in energy between the "~h and the ".15 slates of
the proton plus the hydrogen atom system. A ~ a time I .. r ll/ Il/o:, we ge t
molecule and are associated with n hydrogen atom initially in nn excited state.
Figure 5-7 shows a few of the possible potential energy curves corresponding to
excited electronic states of li t. We shaH e.'(piain the designation of the slates
later on. and the elcctron ha.s jumped w the inC<lming proton, since the system corres(lOnds to the
wa ve funetion "'2. A~ a time t _ 2rh/IlE, the electron is back Ilbou~ iUs original proton.
EXAM/'Ll:: 5. 1. Discussion of the chargtH!xchangc collision Ii + 11 + ..... 11+ + II. Therefore we may say that "'hile thc projectile proton P2 is passing near the target proton
Ill, the eleetron jump!! back and r()rth from one proton to the other with II. period
Sofu fioll: Suppose that II beam of ras~ prolons, or H + ions, passes through hydrogen gas
in the alomic state (for which the temperature must be at least 2400"K and the pressure p .. 2rf1 / IlR - h/ IlE.

190
For electron caplure to occur it ill necessary that, when the incoming proton 1'21e801'(:8 tbe
target proton behind, lhe electron be near 1'2. At the energies shown in Fig. 5-8, the pro-
12
jectile proton 1'2 must pass very close (abou t 10 - m) to the target proton Pl. We 1llny
assume that lhe disturbance of the electron wave function occurs only while P2 is within
a section of the IllI.th, of length Q.
If the proton's velocity is P, the time during which the interaction takes place is r - a/o.
Suppose that a maximum capture probability occurs at a ve locity ~I. The time of inter~
action is 1"1 - 0/"[, The nc;o;L maximum cap ture ]}robability must occ ur at time
1" 2 - Tj + P,
80 that the electron has time enough to perform an extra complete o5cillation and agai n
cnd up close to the projectile proton. Thus ') - ~2 - ~I or
Therefore the difference (I / U2 - l ip ) between successive mllxima must be a constant
\'alue. Experimen tlllly, it i~ found to have 1111 averllge value of 6.6 X 10- 7 m- I s. There-
fore we obtain
at:.E .. 10- 2 7 mJ "" 6.3 X lO- i meV.
The quantity t:.E (that is, the energy llepllration bet"een lhe ,,:111
and the ".Is curves)
is not fixed, since it depends on the SCl),ll.ration of the protolls (~ Fig. 5-6). Similarly,
the quantity a ill not well defined. Taking an average value of 10 eV for t:.E, which ill
reasonable according to the curve of Fig. 5-6, we have that (I .... 6 X 10- 10 m, or about
six times the molecular diameter, which is alw a plausible value.
A more detailed analYlli~ requires a theoretical calculation of the quantity (I t:.E instead
of the estimated values we ha,\'C given, T he agreement with eX[Jerimcntal resull$ is fairl y
!!-Rlisfactory.
f; X AMPL 5.2. Calculation of the ground-stAte energy of nt using the waye functions
gilen by Eq. (5. 2).
Solu lio" , The hamiltonian operator of t he moving electron plull the two protons,
Burned at rest, is
(5.3)
where the fif!lt term is the kinetic energy operator of the electron, according to Tllble 2- 4,
an d the last three terms give the potential energy of the ion, as indicated in Eq. (5.1 ).
When we designate either of the two wave func ti ons tf - JI +
J 2and Jodd - JI - tf2
by J , the average energy of the electron in lit, nccording to Eq. (2.51), is
E _ N* HtfdT.
(5.4)
N',d,
Let us assume for simplicity that the two atomic wave functions tfl and 'f2 correspond to
the same atomic ~tate of energy . For example, in the ground ~ta te of Ht the two are
Is hydrogenlike wave function s. When J I and J2 are real (IS they are in the CILSC of Is
po
(5,2 5.3) MokcuWr orbilall oj dio/omit moIufu 19 1
wave fUllctions), a straightforward calculation, using Eq. (5.4) (which we omit) allows
ua to find the avcrage energy of lhe electron as
,
E _ E+ _'_ _ AB, (5,5)
4..-eor I S
where the l>O!iitive sign corresllOntis to '/1._ and the uegative sign to Jed<!. In this equa--
tion S - fJ IJ2 d~ is called the (Jt;tTlap in/twal, ,,hose value depends on the extent to
which the atomic orbitals JI and J2 assoeiate<i with different protons overlap in space;
that is, the htellt to which JI and J2 have appreciable values over the same region of
space. Obviously S is a function of the separation r of the two prot01lS and increases as
r decreases. Also
The integrals 11 and B arc functions of the nuclear separation, r. A plot of E, given by
Eq. (5.5), as a function of T yields cUrl'es similar to thOlle in Fig. 5-6. We thus get two
l>OBSiblc energy states, as had been predicted Oll an intuitive basis, with J.~ ... corrcspond-
ing to the lower energy.
In Eq. (5.5) the fif!lt term gh'es the energy of the atom formed by one proton and the
electron aud lhe second term gives the repulsive energy of the t,,o protons. Also II is the
attracti ve energy of the electron and the other proton, and Blind S are pure quantal
terms that do not ha\'c a classical anslog. Note that B is alJpreciabte only if tfl and J~
substantially overlap. If the overlapping of JI and "'2 is negligible, both Band S are very
small and the energy is B _ f;. + e2 / 4nor - A, which when plotted as a function of r
does not show a minimum. [-[cnee it is the overlalJping, combined with the symmetry of
the wave function, which gives rise to a stable molecule.
1i.:J ." ulf!f!.ular (Jrlll/aill of Diaiolnic It'fJlef!ul~1I
After the !-I t molecule, which hM ollly one electron, the next-simplest molecule is
one which hM only two electrons, such as H 2 The analysis of this molecule is
M- very similar to that of the 1:I t molecule, but with some important d ifferences. As
800n as we have more than one electron, we must invoke the exclusion principle,
which, as may be recalled from the atomic case (Section 4.3), requires that We take
into account the spin of the electrons as well as their orbital m otion.
Let us s tart by first discussing the orbital motion of the electrons. In a diatomic
molecule (as well as in any linear molecule) the electrons do not m ove in II. central
field of force and therefore the :mgular momentulll L o f un electron d oes not remain
constant during the motion. Let us designate thc line passing through the two
nuelei as the Z-a.xis ( Fig. 5- 9); the resultant fo rce on an electron always passes
t hrough the Z-axis. In other words, the force is axial. In this case the torq ue on
the electron relative to 0 is perpendicular to the Z-axis and therefore the com-
ponent of the angular momentum of the electron parallel to the Z-axis, L .. is
oonstl\llt. This component o f the angular momentum, as we know, may have the
values L. = m1h, where ml = 0, -I, 2, ". The sign of ml determines the
sense of rotation of the electron about the Z-axis; however, the energy of the elec-
 p

,192 (5.3 5.3) Mokcular OI'bifab of diaJomic molulu

tron is independent of the sense of rotation. Therefore, in order to specify the s tate
of an electron, one need give OIlly the absolute value of m, (that is, A = Imll).
The d iffcrcnt angular momen tum states are designated according to the following
scheme:
m, : 0 I 2 3 z ,
A: 0 j 2 3 I
Symbol: rT
I
I
Thus, cxccp~ for rT-slates, all other angu- I
I

lar momcntum statcs arc doubly dcgen- I
erate because of lhe double sign of mi. In N1 t<"' ,
addition, in each of the above st.ates the
electron may have its spin up or down
,.
I ' ,'1
,, z
relative to the molecular axis (correspond- 0+ i (a) Molecular orbitals relllJJling from II lltomic orbitals
ing to TIl. = +i and - i, respectively)
Ii I
I ' I
so rT angular momentum states can ac- N,( N,j
commodate two electrons, one with sl>ln I I
up and IUlother with spi n down, Ilnd the (-I co,
remai ning states "If, a, <1>, . , can accom- Fig . 5--9. Electronic orbital angular
modate up to four electrons each, two momentum in a diatomic molecule.
with spill up and two wilh s pin down,
For molecular orbital stalcs of the electron we shall use the notation Ant (that is,
11711, '/ttl/, alii, etc.), whcre nl serves to indicate the atomic orbitals from which
each of thc molecular orbitals has been formed by linCllr combi nation. Each of
these molecular orbital states corresponds to a different cncrgy.
In thc C/l.8C of molecules composed of two identical nuclei, such as Hi nnd 1-1 2 ,
called Iwmoltuckar moleculcs, t.here is an importallt symmetry to be considcred. z
T hese molecules have a ccntcr of symmetry 0; the probability distribution of an
(b) Mol~ulRr orbit.aLs resulting from p, atomic orbitaLs
electron must be the same at. points symmetric\\lly located relo.tive to O. T herefore
the wave funcliOIl of the elcctron must be the same at symmetrical poinlO! or must
have the same value but. oPlXlSite signs. This is, for example, tbe situation we found
for Hi, corresponding to wave functions Y-~ and Y-odd, illustrated in Fig. 5-4.
Angular momentum s tates described by wave functions of the type Y-",",,, arc called
g-states and those describcd by wave functions of I.be type Y-odd arc called u-states z
(from the oerman gerMe, or even, and ungerMe, or odd). Thus for homOlluclear
molecules we have statcsl1" 11., '11"" 11".. , etc. This explaill8 thc notation we intro-
duced in Section 5.2.
To understand how two atoms bond to form a molecule, it is csscntial to know
the space variation of the electron probability distribution corresponding to each
elcctron angular momentum state. This hM becn done for the rT~ls and 11:l s states
of Hi in Fig. 5-5(b). T he procedure to be followed in gencral is t he same as ill the
case of H i. We start by considering the two atoms separated a very grcat distance z
and guess how the atomic wave functions Y-I and Y-2 combille linearly to form a (e) Molecu!lU' orbitaLs m.ultinr; from v. or P, IllOOIic orbitals
molecular tctU.oejulidion or orbital y-, as the two atoms get very close.
Figure 5- 10 illustrates a few molecular wave fun ctions or orbitals resulting from Fig. 5-10. Molecular orbitals in homonucleo.r diatomic moleculea.
linear oombinatiOIlS of some specific atomic wave func tions (or atomic orbitals).

194 Moiuule8
Moleo:ule
2p - -----<.,.::-
_
,
======= .
~'::=======""
---<'
------,,'
------'"
Fig . 5-11. Electronic energy levels
in homonuclc:lT diatomic molecules.
_ _ ____
,.------<: ------",
In this figure only the angular distribution of the wave functions is shown. Fig-
ure 5-1O(a) shows the case in which we combine two s atomic wave functions which
are spherically symmetric. The two resulting molecular wave fUllctions obtained
by combining 0/11 and "'~ in t.llC forms -I -2 are shown to the right ; these cor-
respond to lheuQ and u" states already discussed for Hi. In J'jg. 5-lO(b) we have
the two Illolecular wave functions which result from combining two p~ atomic wave
functions, and in Fig. 5-1O(c) lhose which result from combining 1>% or p~ atomic
wave functions. AU these {unctions are modulated by the radial part of the wave
function. Thus, for example, (f~ functions resulting from Is, 2s, etc., atomic or-
bitals have the same angular distribution but differ in their radial variation.
Those molecular orbitals which have a nodal plane (indicated by a dashed line)
perpendicular to the line joining the two nuclei are antihonding, and the others
are bonding. The sequence of the difTerent energy levels for a molecule are shown
schematically in Fig. 5- I 1. The actual separation and ordering of the energy
levels may vary from molecule to molecule, and for each molecule they depend
on the internuclear distance.
5.4 Electronic t-onfiguralion of Sollm IJiflton.ic i'toleculeN
Let us now analyze some simple diatomic homonuclear molecules. We have already
discussed the simplest one, B t, in Section 5.2; we know that its ground state COIl-
sists of one electron ill the er~ l s state. Next we con-
sider the H 2 molecule, composed of two electrons
and two protons (Fig. 5-12). This molecule is still
sim ple enough so that it is possible to annlyze it. in
great detail without actually solving the Sehro-
dinger equation. T he tutal electrical potential
energy of the system is
(5.6) Fig. 5-12. The 9 2 molecule.
po
(5.4 M) Elec/ronit configu.ra/ion of some diatomic mo/e(u/es 1[15
'rhe first. two terms correspond to the in teraction of clectron el with protons PL
"
";
and P2, the t hird and fourth to the interaction of e2 with PL and P2, the fifth to the
repulsion between the two electrons, and t he kist to t he repulsion betwccn the two
protons. Note that because of the identity of the two electrons we can no longer
say thnt electron eL belongs to protOIl PL a.nd electron e2 to proton P2. The atoms,
in a. sense, hnve lost their individuality and instet,d we have a lIew entit.y: a
molecule.
The next step would be to set up the Schrodinger equation corresponding to the
above potential energy, proceedi ng as we did for the Hi molecule in Section 5.2.
However, we s"hall not pursue this method; rather we shall take advan tage of lllc
u~
discussion in the preceding section. We may th us consider that, according to the
exclusion principle, the two electrons can be accommodated in the bonding level
ergls with opposite SpillS, giving the configuration (eruls)2. Both electrons are in a
bonding stlLte ILnd give rise to a stable molecule. T he molecular energy of this
configuratioll as a function of the internuclear distance i~ given in Fig. 5-13. The
C<luilibrium separation of the nuclei is 0.74 X IO- LO In and the energy of dissocia-
tion into two hydrogen atoms in their ground states is " Ai6 eV. If the two elec-
trons have t.he same spin, one electron must be in the bonding state ergls and t he
other in the anUbonding state u:ls, resulting in the configuration (er uIs)(er: Is).
The nntibonding efTect dominates the bonding effect, and no stabl e configuration
results, as ijhown in the corresponding eurve of Fig. 5- 13, which has no minimum.
e"eV
Fig. 5-13. Electronic potential energy as a
func tion of intcrnuelelH separation for bond-
ing and antibonding states in tb
'. -
O.74X 10-10 m
o+-+-I\-j----t:;3~_l3'--t4-r, 10-10 m
Next we mlly consider Hci, which has three eledrons. T wo electrons arc ac-
commodated in the bonding state eru!s and the third in the anlibonding state
er:l s, so that the configuration is (erQ ls)2(er:l s). The result is a stable molecule
with a dissociation energy equal to 2.5 eV. The moleeule 1-1 2 also has three elec-
trons, but because the nuelear charge is relatively small, its dissociation energy is
also very small and its lifetime is very short. However, it has bccn observed
spectroscopically.
 p

I .. Molteultl (5.4 5.4) 197

TABLE 5-1 t:leclrolli c Conrig ur.. tion of HomOlluclear Diatomic Molec ul es orbitals and their spins arc pa.rallel instead of opposed. This cha.racterislie of 8 2
alld O2 is due to the fact that 1f-()rbitals can accommodate up to four electrons,
two with spin up and two with spin down, while thcsc molecules have only two
electrons in that energy level. From the atomic case (Section 4.3), we recall that
the repulsion among the electrons favors the most antisymmetrie space wnve func-
tion. 'fhi!> requires the most symmetric spin wave functi on according to the exclu-
H. '.00 ':;, sion principle, which means in this case that the two electrons have their spins
parallel. Since the resultant spin of O2 is olle, the oxygen molecule has a permanent
magne~c dipole moment, thereby explaining why oxygen is II paramagnetic gas,
H,
ITIl O.H
while most homonuelea.r d iatomic gases arc diamagnetic. We mn.y also expect that
li e. 1TIl[i] .... ,::.
the stability of the molecule will depend on the relative number of bonding and
Mtibonding pairs of electrons. For example, we hnve indicated lhat I-I C2 has t he
same number of bonding and antibonding pairs of electrons and is not stable. The
ITIlITIl Not ,lable same happens to 80 2 ; therefore both molecules arc unstable. On the other hand,
the stn.bility of .N:, O 2 , F 2, and Ne2 (as measured by t he d issociation cllergy)
J.i. [i]][i]][i]] ."" :,67 decreases because the d ifference betwccn bonding and antibonding I)airl! for these
molecules is 3, 2, I, and 0, respectivcly .
.... The component of the total orbit!!.l n.ngulur momentum of the electron along the

., [i]][i]]1ill1ill No~ oI.able ' l:,

moleculnr axis is given by !If,}l , with M /, = L ,"1n/i. The energy of a given state
[i]] ITIl ITIl ITIl [jjJ ., .." '!:, depends Oil t he value of A = 1Md. Depending 0 11 whether A = 0, 1, 2,3, ... , the
state is designated by the symbols t, 1'1 , 0, <1>, etc. Given th nt S is the resultant
c, 1.31 '::, spin of the electrons in the molecule, the symbol of a state or term is 28+1 ,.,. The
1TIllTIllTIllTIlillill ground-1State terms of the molecules in Table 5-1 :u-e shown in t he l[l8t column.
When the two nuclei composing a molecule tu'e different, such Ill! in t he case of
1TIllTIllTIllTIlillilllTIl '.00 '!:,
IICI, CO, and NaCI, the molecule is Clllled Mlerolmclear. In these molecules the
coulomb interaction of each nucleus with the electrons is different and the molecule
0, 1TIl1TIl1TIl1TIl1illD1lll[jjJ '.09 1.2 1
nO !ollger has a center of symmetry. Thus, although the electronic states arc still
('nllc<1fT, 1'!', oJ, . , etc., they !Ire 110t d:l.~ificd as g !lnd 1.1. In general, 1\8 we ~I\d i
1TIl1lll1TIl1TIlillilllTIl[iillJ ':;,
" 1.-11 call.'d at the beginning of the ('hapter, onl y the electrons in the lMLunfilk>d shell in
each ato m arc considered when one ill discussing these molecules.
Let us t!lke, as an example, the case of NnC!. T he problem consistA in describing
the lIIotioll of the II electrons from the sodium atom and t he 17 electrons from the
chlorine !110m ill t he electric field produced by the nuclei of Na !lnd Cl at their
T he 11 02 molecule has four electrons. two in the bonding state ITg l S and two in t'!quilibrium scparation (in the gas phase) of about 2.5 1 X 10- 10 m. To simplify
the nnlibonding state <1:1 5; l haL is, (<1,l s)2(0'!ls)'. The result. is that no stable the problem, let us assume t hat, since the electrons in dosed shells arc tightly
configuration is produced. This explnins why helium is :l monatomic gas. How- bound to their respective nuclei, thcy arc not affected by the prcscnce of a second
ever, an excited l-I e2 molecule may be formed if Olleof Ihcu! IS electrons is excited nucleus. Also, in line with O\lr l)recc<ling disc ussion, those electrons which arc in
to the bond ing stil.tC Uu2s, TCi'iulting ill (ug ls)2 <1:15 ug 2s. unfillc<1 !'hells and which have their spins eouplc<1 arc not expected to participate
T nble 5- 1 !!hows the electronic configuration of the homonuulcnr diatomic mole- strongly in the binding of t hc molecule. Tlms we arc left with onl y two unpaired
culC!! up to Nc~, The table n150 indi('atcs the binding energy nnd the bond length electrons, t he 3~elect ron in N!~ llnd one 3p-c\edron in CI.
of t he ground !:ltale of these molecules. Some interesting features Cl!n bc sccn in Applying the same logic ns for homonuelear molecules, we could s!ty t hat a stable
this tl1ble. In gener:ll, molecul:lr binding rc;;ults when twO electrons with op]}()sile 8tructure ill produced when the two elC(trons !lre conccntratC(1 in the splice betwecn
spins eonCCn lrll.lc ill the region bctwcclI the two combining atoms; t hat is, they the two atoms. Uowevcr, si nce the nuclear charges arc difTerent, the electronic
occupy bonding molecular orbitals. This, however, is not a strict rule, sinoo !-l et distribution is IIOt symmetric. In the case of the NaCI molecule, the electronic
1m.'! only three electrons, and in B2 and O 2 , the last 1):lir of eleclrt:lns :Ire in '/l"- charge is d isplaced toward the Cl nucleus, sinoo the CI nucleus produces n. stronger
 F

198 Molecuks (5.4 5.4) Eiec/ronu: configura/ion of 30~ diatomic moleculet 199

attractive field. This result.;; in a molecule which has an uneven charge dist.ribulion TAULE 5-2 Dissoc iation Ene rg ies D, Rond Lengths "0, and Elec tri c Dipolc Mo_
and which is therefore polarized. The cleclricdipoic momeut of NaC! in thegasoous m ents I) of Some Diatomic Mol ec ules
phase is about 3.0 X 10- 29 m C. Tf the 3s-electron of N a were COffil)\etc!y trans-
ferred to the Ct, the molecule would be a dipole of charge e = 1.6 X 10- 19 C and Covalent Ionic
length equal to the equilibrium separ8Lion 2.51 X 10-\(1 m, thus having a dipole
Mol~ule D, eV ro, A p, D Molecule D, eV ro, .~ p, D
moment equal to 4.0 X 10- 29 m C. We conclude therefore that about 75% of the
electronic distribution of the valence electron in No. is displaced toward the Cl H, 4.48 0.74 0 KaCl 3.58 2.51 8.5
atom and we may consider t.he molecule as being cOllll>osed of two ions held to- Li 2 1.03 2.67 0 Hel 4.43 1.27 1.07
gether by their coulomb attraction. We may express this situation by writing 0, 50s \.21 0 LiB 2.5 1.60 5.88
Na+Cl-. This type of molecular binding is called an ionic oond, while the situa,.- N, 7.37 1.09 0 KBr 3.96 2.9 -1. 1.29
tion described earlier for homonuelenr molecules, wi th a symmetric electron dis- el, 2.47 1.99 0 KF 5.' 2.55 860
tribution , is called a cooulen/ OOnd.
H[ 3.06 1.61 0.38 CsCI 3.7G 3.06 9.97
CO 11.1] I.] 3 0.]2 KCI '1.92 2.79 80
NO 5.3 1.15 0.]5 KI 3.0 3.23 9.24
t:, eV
, The molecules are grouped according to the dominant character of lhe bond. Elcctric
N,,+ CI di]>ole moments are expressed in /.hbyes (D). One D is 3.3 X 10 - 30 m C.

The molecular orbital or wave function of a hetcronuclear diatomic molecule

cannot be of the type givcn by Eq. (5.2), which treats the two nuclci in a sym-
.f.f!.-_____ !..:~..!:.~
~!!.
metric way. Hence (if A and B designate the two nuclei) instead of writing Eq. (5.2)
for a bonding molecular orbit, we must write

>/I = >/1,1+ >4n,

- 3.58 --
o 2.51 x 10- 10
" IS 2(1
Fig. 5- 11 . Potcntial energy curves for NaCI and Na+CI - .
Figure 5- 14 shows thc potential energy of the sodium-chlorine system (in the
gas phase) as a fun ction of the internuclcar se)aration. At greflt distances, the
two interacting systems are the N:~ and Cl :l.toms :l.nd their intemction is very
small, so th:l.t the potential energy is practically constant. At. a separation of
about 12.5 X 10- 10 Ill, the charge trallsfer from Na to Cl begins to entcr into
elTect. As the separation is furthcr reduced, the interaction ]>otcntial cncrgy rc-
sembles the attractive coulomb I>otcntiai between the ions Na+ and Cl-. But. at
very small internuclear distance the IXlpul,;ion oot.ween the nuclei and tllC closed
shells of the two ions incrcascs, offsetting the iOnic 9.ttr;lction between ~a + and
Cl-. T he minimuill of the ]w tenlial energy or equilibriulll I>osition cOITesl>OlH.ls to
a separation of 2.51 X 10- 10 Ill.
where >/I ... and >/1 8 are the atomie wave functi ons of the electron in relation to each
nucleus. The paramcter ~ is ehoscn so that the calculated energy agrees wi th the
experimental value. Depending on the value of X, the clectronic distribution is
enhanced in the region between the two nuclei or toward either of the nuclei. I n
HIC fi rst case the bond is predominantly covnlent and in the second case it is mostly
ionic. For most hetcronuclcar diatomic molecules, the situation is intermediate
between the pure covalent bond and the pure ionic bond. In general, the more
ionic the bond is, the larger the electric dil>ole moment of the molecule. For e);-
ample, in the CO moleculc, in which both nuclei have similar charges, the ionic
character of the bond is less noticeable than the covalcnt one. This is made evident
by the relatively small clectric dil>ole momellt, 0.40 X 10- 30 m C, of the molecule.
Table 5- 2 gives th('" dissociation energies, bond lengths, and electric dipole moments
of some diatomic molecules, and also indicates the dominant character of the bonds.
EXAMPI.E 5.3. Discussion of the Morse potential.
Solu fiQ": An empirical e);])ression which gives, with somc accuracy, the potential encrgy
or a bound stllte of a diatomic molecule for 9. given electronic configuration i ~ thc J/Qr3e
pcnemial,
(5.7)
where the constants D, a, and TO arc adjustable parameters charflctcrisi ic of ellch molecuI('.
 ..
'2IJ(} (5.4 5.4) EifrOllic roIljigwtlliOIl of ~ dialomi( mo/UUk6 201

The graph of E,.(r) i! shown in Fig. &-16. From thii! tahle we sec tha~ we have enough wa ve functions to make the followi ng molec-
T he min imu m of E" is obtai ned by find ing ula r SlRte~;
dE.!dr and equaling it to ~cro . T hus JIl L _ 2, M!J - 0: ' t.-alale
ML - 0, M !J- 1,0: 32;_stale
.lI t - 0, .I/!J - 0: II-atate
which require!! tha~ e-ej'-'ol - I or r - ro,
indicating that 1"0 is the equilibrium separa- T hus Ihert'lanl three j)()SSible terms corresponding to the configuration (1"211) 2, of "'hich
tion . At lhe minimum the va lue of f.:,. is the grouud stale is th ll t of higher multiplicity, 32;. T his is the ground 8tRie of Ih and 02.
teTO. For \'cry large r t he exponent ial is neg-
ligible an d B" tends to the co nstant value D. EX".MIU~ 5.5. DiseuSllion of th e potential encrgy of a diatomic molecule for the case
Thul! we could ~Ry that D ;3 t he (!Ilc rgy re- of ionic binding.
quired to scparatc or d i'>S()(': iatc the molecule
if it is init ially in the stille of m inimum &'11lIion , ,\ n empi rical expre!!$ion which gil'e!! a fsirl), accurate descript ion of the ]loten-
1)(I\cntiai energy. This maller, howe\'cr, has r tia l en(.'rgy for ionic binding is
to be considered more tardully because of
the sO-<:lll1ed ur".poinl !if,raliofUlL ener"v
(SCfl Section 5.8).
0 TO
Fig. 5-1 5. M orse potential.
. . . . .
.' rV .
--+_
4l1"toT
, (5.8)
For small T, B, tends to the value 0( 1 - eo.o)2 instead of to llIhmty, !U\d tIllS L~ 0.
limitation of the l\Ior!le IlOtclltial. To ob tai n the mean ing of the constant. (I we must. The first term is t he IllIre coulomb attraction between the ions and the sceond term ac-
wai t until we diseu.'l3 molccular "ibration! (Example 5.7). counts for the repulsion of nuclei and closed shell~. '1'h(.' exponent 9 was chosen because
it I)roouce.!! Ihe bes~ fit 10 experimental data by an inv(.'rse r O function. l3(.'cause the
F.,y/l.HPU,; 5. 1. Determination of the pOiISible terms of the ground state of !!Orne of eecond term depends on , - ', it falls off "cry ral)idly with the nuclear !leparation and i!
the moleeules in Tal>le a-1. importRnt only aL slllllll dibtances. The equilibrium !Ie]lllralion r is obtained by findinJl'
501.. liOlI' When a molecular orbital XIII h~ its com!llete quota of electrons COml)ati?~,e th e minimulll of R . Thus
with the exclu.~ion priucill]C, the only pos;:nble stille IS .11 L - 0 and S - 0 or stRte ....
l\lokcules 112, Il c2, Li2, llc2, C?, and 1~2, ill Table 5- 1, l'avc thcir.upp~:rmost molecular
orl>itals filled and their ground state is Il: . If only one electron eSlsts In the u ppermo~t.
molecular orbital Xtll, obl'ioU!dy A _ X and S - i. T his is the situation for If; and lie!,
which have X _ 0, and the ground-state term i~ 2L Different possible terms o~cur when giving b _ e2 r3/ 3&... 0. T he corrtspondi ng energy E. at the minimum, de~ignated D"
a moleeular orbital i~ not completely filled but has more than one electron, as III 112 and is D, ... -(S/ 9)e 2 / 4noTo, This is the diulH:wlioll ellUl1!1 of the molecule, It is equal to
o both of which ha"e the I"Qnfiguration (-r2p)2. The molecular orbital -r2p is made Ollt the energy required 10 di.S80ciale the moleeule, initially in ils ground 8Iat(.', into IWO ions
of2~tOmic wa,,(.' functions with >Il, _ 1. Al~o m. - i. T hus lhe possi,ble ar,rlu~gc at r(.'st and il('parated all infinite distance, III the case of :-IaCl, D, gi"e~ the encrgy re-
meni.S of quantum numbt'u (or atomic orbita\.i) compatible with the exclUSion pmlc,!)le quired 10 f!Cparate the molecu le into the ion ~ :-Ia+ and CI-, The energy of the systenl
ar(.' given in the following table, in which the symbols corrcspond to the wave func tIOn fo rmed by :"'1\+ and Cl- lit infi nite scparation corresponds to the dashed line in Fig. 5- 14.
(rII" m.h(m" m.h Selling TO _ 2.5 1 X 10 - 10 m, \\'(.' find a dissociation en(.'rgy for l'\aCI of 5.12eV. Ilo\\'_
e\'er, w(.' a.re intercsled in the energy required to di!li!OCiate NaCI into neuLral atoms, such

~' +1
0 as:-la and CI. An energy ('(Iuallo 5. 14 eV is required 10 ionize a Xa atom , while when the
- I
.II,. ion CI- is formed an energy equal to 3.i2 eV is rele/L.oetl. Therefore, th(.' @y~lem formed
+, (1 ,+)( 1, I by Na+ and CI- at infinite SCJlllration has an energy in exc(.'ss of the syslem Xaaml CI
at in!inite scparation, equal to 5. 14 eV - 3.72 eV _ 1.4 2 eV.. Thill mean ~ Ihat the dis-
+1 sociation energy D. of XaCI when it is SCllsrated into neutral atoms i~

0 {I, - )(- 1, - )
(I , +11 I, I (1, + )( - 1, +) Do" 5.12cV - 1.42 (.'V - 3.70cV,
(I. -)(- 1,+)

- I Which is somewhat larg ..., than the experimental \'Il lue of 3.58 e\'. One can obtain a IJetter
fit to experimentsl data if the rellub'h'e iu\"(.'rse, term i ~ replaced by an e~ponentiallerlll
-, ( 1, +)( I, I ha,'ing the form b exp (-,ro) .
 p

202 Mokcuks (5 .5 5.5) Polyalomit moleculu 203

G.G 'tlllIttiomie .lIoleculpIf
For 1lI01(!Culcs with more than t.wo atoms, an important. new clement. enters into
the annlysis of el(!Ctronic motion: the geometrical arrangement of the el(!Ctrons and
the nuclei (or in other words, the molecular symmetry). We must remember from
the diatomic CMC Ula~ bonding is favorl!<i when the bonding electrons can fit
within the region joining two atoms. This rl!<luircs that the n.tomic wn.ve functions
which pcrtain to the two atoms and which m::tke up Ule molecular orbital extend
or ~overlap~ ns much ns possible along the line joining thc two nuelei, favoring the
condition in which a pair of electrons (one from each atom) arc l.'O ncentratcd be-
tween the two atoms. We may state this requirement of ~ml\.:(imum overlal)ping"
of atomic wave functions as follows:

A bend between lwo atom, o(cu" in the direction in u:hich the reqH!divt
alomic WOt.'t funclion, making up the molecular oruitat are concentrated .' i g. 5-16. Elcctronic distribution in the Fi g. 5-1i. Electronic distribution in the
or OIleriapi the strength of the bond depend8 011 the tlegree of OIIeriapping H20 molecule. NH3 molecule.
of Ihe atomic =efunclions.

The principle of maximum overlap is very helpful when we wish to determine axcs, Occu l)ying Pz, Pv, and ]). statcs, so that the K H 3 molecule has IL pyrumidal
the shnpe or gl.'Ometry of a molecule. Let us take the cnsc of the water molecule, strudure, with the N atom at one vertex and the H atoms at the other vertexes
H 20, for example: it contains 10 electrons and three nuclei. III the o.~ygen atom ~orm ing the base (Fig. 5-17). The rulgles at the N vertex of the pyramid arc JOi.30
we mny f1gnin forget (in ll. first ll.1)prol:imalion) all electrons except the two unpaired mste~ of 91! because of the repulsion between the If atoms. The pyrzunidal struc-
1>-cI(!Ctrons in the L-shell (Fig. 4-3). These two electrons, which have parallel ture g~vC8 n se to an eleetric dipole moment of 5.0 X 10- 30 m C dirccted along
SpillS, as shown in Fig. 4-3, must differ in their orbital motion. Remembering the axIS of the pyramid. The dipole moment would be zero if the 1ll01(!Cule were
Fig. 3- 11 , which shows the angular distribution of the p-electrons, we may assume plrular.
that one electron is concentrated along the X-axis and the other electrOIl along the The carbon atom is illtcrcsting. In its ground state it has only two unpaired
Y-axis; that is, the unpaired 21>-electrOn!! occupy states pz and p~. (The remaining 21>-eleetrons, and this cannot. el:plain many compounds of carbon. One of the first
21>-electrons of 0 nrc along the Z-axis, or P. state, with their spins paired.) The excited states of carbon, as shown in Figs. 4-8 and 4-10, cOllsists of one 2s and
two H atoms, each with one Is electron, !tre located so that their reSI)eetive elec- three lllll)aircd 2p-electrons, with their orbitals arranged Il.8 in Fig. 5-18(0.). The
trons couple in the best possible wny (~hat is, with mal:imum overlapping of their 2p.clcctrolls would act similarly to those of ammonia, but the 2s-e1ectron {because
wave functions) with the two unpaired electrons in O. T herefore we conclude that,
for maximum overlapping to occur, the two 1-1 atoms must be located on the X-
and l'-axes, respectively, at CQual distances from the 0 atom. This results in a
molecule with a right-allgle shape, as shown in Fig. 5-16.
Note thaL in Fig. 5-16 the distribution of the p-elcctrons from 0 is not drawn
e:mctly equal to that shown in Fig. 3- 11. The reason for this is that the presence
of the H atoms deforms, or pol:l.rizcs. the motion of the p-electrolls from 0 some-
what. Also the angle between the two 0 - 1-1 bonds is slightly largcr than 90"
(nctually it is 104.5) because of the repulsion between the two H atoms. A de-
tniled calculation shows that the hydrogen Is-clectrons arc pulled toward the 0
atom so that the centers of m!WJ of the negative and positive chnrges do not coin-
cide, producing a I>olarizcd molecule with a resultant electric dil)olc moment of
6.2 X 10- 30 m C, along the line bisecting the bond angle. Obviously, if the H 20
molccule were linear, the dipole moment would be zero.
(a) ~. I'" P, . and PI wave funeliOlUl (b) ~1l3 hybridited "'"'e functiom
Next let us consider the ammonia or Jl;" H 3 molecule. The three unpaired 2p-
elcctrons in the X atom (see Fig. 4-7) arc concentrated along the X-, )' ., and Z- F i g. 5-18. Wave functions resulting from sp3 hybridi.r.ation.
 po

(.5.5 5.5) PoI.yalomic mokcu/.e, 205

(&) ~p~ hybridiled \\"~\'e ["nctions (1)) J', WR\"e rllnrtiQII

(., ( b) Fig. 5-20. Wave functions resulting from Sll2 hybridiZAtion.

Fig. 5-19. Loesliled Sp3 molecular orbital bonds in (a) methsoc, (b) ethane.
Similarly, the ethane (or I-l aG--CH a) molecule hM the structure indicated III
of its lack of direetionality) would not produce a bond of the same strength, mak~ F ig. &-19(b) . III t his molecule the two carbon atoms are held together by the over-
ing it difficult to explain moleeulcs such 88 methane, CH 4 It is possible however, iflPI)ing of two hybrid Sp 3 wave functions. This is called a u-bond due to its sim.
by means of the teehnique called hybridization oj wave junctioru, to produce new ilari\,y to the situation of u-orbitals ill diatomic molcculcs. '
atomic wave functions oriented in the desired direetions. The one 2s and the three It is important to reoognite that. hybridization applies not only to carbon but.
2p wave fun ctions of carbon do not have exactly the same energy, but the difTer~ ~o anr/tom or ion which hM the same electronic configuration. For example, the
ence in their energy is very small. By making proper linear combinations of the Ion N hM the stune electronic arrangement ns carbon and the structure of the
four functions, we may obtain new or hybrid wave functions, all corresponding to radic~ X +H4 is similar to that of CH 4, with N+ replacing the carbon atom.
the same energy and having a pronounced maximum in any desired direction, A . Bell.des Sp3 hybridization, there are several other possibilities of hybridization
possible set of linear combinations of the s, p~, P., and P. functions give four new lIlc\udlllg wave functions whose 8..llgulo.r mOlllenta have values higher than one
hybrid wave functions with ma:"ima which point toward the vertexes of a tetra- We shall discuss only Sp2 and sp hybridization because of their importance. I ~
hedroll, M shown in Fig, 5- 18(b). The direetions along which the new wave func.- Sp2 hrbri~jzation the s, P1, and p~ wave functions combine to produce three wave
tions have their maxima form angles of 109"28'. They are expressed in terms of fun ctions 1I~ th.e Xl'.~lall~, with thei.r maxima pointing in directions making angles
the sand P wave functions 88 of 1200, as IIldlcatcd 11\ Fig. 5-20, 1 hcsc wave functions are expressed in terms of
the sand p wave functions as
Vtl - Hi! + p~ + Pw + P.) ,
Vt2 = ;(s+ p~ - P~ - p.),
(. 9)
Vt3 = ;(s - p~ + P. -
P.),
Vt4 = ;(s - P1- p~ + P.)
(5. 10)
This type of hybridization is designated by Bp3. Note that because sand p wave
functions correspond to difTerent values of the angular momentum, the hybrid
wave functions do not describe states of well-<iefined ang ular momentum,
Kow lct us consider tho. methane molecule: CH 4 , We conclude that the maxi-
mum strength of the bonds is obtnincd when the Is-electrons of each hydrogen
Th,e fourth electron occupics :l. p. stale. This is the type of hybridiznlion f'C-
atom achieve maximum overlapping with cach of the four Sp3 hybrid wave func~
i~lrcd to explain molecules such as ethylene H 2C = CH z, shown in Fig. 5-21.
tions of carbon, This results in the tetrahedral molecule shown in Fig. 5-19(a),
e double bond between the carbon atoms results from lhe ovcrlapping of one

206 Moltculu (5.5 5.5)
''''
z

Fig. 5-22. Wave functions resulting from sp hybridization.

(.,

(C)

F ig. 5-21. Electronic distribution in ethylene U~iDg Sp2 hybridization: (a) v-bond,
(b) lI'-bond. Fig. 5-23. Electronic distribu-
tion in acetylene using sp hybrid-
jution. (a) Wave functions with
Sp2 hybrid wave fun ction from each carbon atom along the line C-C (that is, a. aWIDlI separated; (b) /7- and
(b) T-bonds.
u-bond) and the overlapping of P. wave functions, which constitute a If-bond, 80
called because of its similarity to the case of If-orbitals in diatomic molecules.
The hydrogen atoma are attnchcd to the remaining Sp2 hybrid wave functions. As T he t hird type of hybridization with s and p atomic orbitals is called sp, and
a result, the ethylene molecule is planar. The doublculf-bond has a certain rigidity corresponds to wave functions s ::I:: pz, which have pronounced maxima in the
which makes it difficult to twist the molecule around the C-C axis. This rigidity ::I::Z-direetions. These hybrid wave functions are shown in F ig. 5-22. Hybrid sp
does lIot occur when there is a single bond, such as there is in ethane, and it has wave fun ctions are required to explain molecules such as acetylene, H ~H
some effect 01\ the molecular properties. Note that t he degree of overlapping in a (Fig. 5-23). The triple bond between the two carbon atollUl results from the over-
1I"-bolld is much less than in au-bond, fi nd therefore 1r-bonds cont ribute leas to thc lapping of one sp hybrid wave function from each carbon atom (that is, a O'-OOnd)
binding energy than u-bonds. For example, 6,33 eV arc req uired to brenk a single and the overlapping of p" and PI' wave functions, resulting in two 1I"-bonds. The
O'"-bond, but only 3.98 eV are nceded to brenk a double 0"1I"-bond into a single hydrogcn atoms are attached to t he remaining 8p wave functions. As a resul t ,
u-bond. acetylene is n linear molecule.
r
208
(b)
Fig. 5-2.l. Electronic distribution in butadiene. (a) Localized Q"-bond~ ; (b) unlocalitcd
,...-bonds.
5.6 Conjugated lUo/eeulell
Let us lIOW consider a cJtlS1l of compounds, called C(JJtjugaied by organic chemists,
of which butadiene (C4H e) is an example. The electronic structure of butadiene
is indicated in Fig. 5-24. The carbon atoms along the chain aTe bonded by u-bonds
using Sp2 hybrid Wltve functions. The hydrogen atoms arc attached to the carbon
atoms using the rcmaining Sp2 wave functions. B\lt irl addition there are four p.
electrons forming .,...-bond8 along the carbon atom chain. 111 conjugated molecules
the .,...-bonds behave in a special way. The 1f-bonding clectrons-one for each
carbon atom- instead of being localized ill particular regions of the molecule, tIS
are the clectron8 in u-bonds, are more or less free to move along the molecule, !'18
indicated in Fig. 5-24(b) by their probability distribution. The "IJ"-electrons RCCOrd-
209
5.6)
(.5.6
.,
s
"
Fig. 5-25. i\Iolecular orbitals for T-elcctrons in butadiene.
ingiy act in So very special way which requires further consideration. For exampl~,
the polarizability of the conjugated. molecules in the direction of the ,carbon cham
is much greater than the polarizability of sat.urated hydrocarbo~8 which have on~y
localized u-bonds and sp' wave runctions. Also the 7-eleetrons mtroduce So certaln
rigidity into lhe molecular structure, 80 that all carbon atoms, lie in a plane.
Let. us 1I0W discuss the wave functions or molecular orbitals of the four 11'"-
electrons. At the bottom of Fig. 5-25, we have schematically indicated the radial
wave function of each 1r-bonding electron when the carbon atoms are all very
distant from one another. When the atoms are very close together, as they are in
a molecule, the possible wave function~ are obtain~ by ~nking pr?per ~inear
combinations of the individual or atomiC wave funcllons. fhe tecJlluque 15 the
same II.S that used for H ,+ and H 2 , but now we hnve four atoms insteadb of .two.
h
Because of the symmetry of the molecule the molecular orbitals must celt er
symmetric or antisymmctric relative to the center of the molecule. The four pos-
/lible molecular wavc functions of the ""'-electrons are designated by flo "'2, "'3,
a.nd
"'4 in Fig. 5-25, and each corresponds to a dilTerent. cncrgy, which increases With
the number of nodes of the wave function. Therefore,!'18 the carbon atoms are
drawn closer, the energy of the system splits into four closely spaced levels instend
 p

2/0 Mohculu (5,6 5./J) 2/1

a Interatomic di$tll.nce

Fig_ 5-26. E:lootronie potential energy of ...-electrons in bult\diene as t\ function of

int.emm)lea r eepa ration.

of two, /l.8 in Ht and H 2 The four cnergy curves arc shown qualitatively in (. J
Fig. 5-26, lUI functions of the internuclear distance. Each energy level call accept
two electrons with opposite spins. Thus, in the ground state of butadiene, the
four 1f-elcctrons occupy the states corresponding to o{I 1 and f2. The next two nearby
states, corresponding to "3
and "'4,
are empty. The resuiling probability distribu-
t.ion of the electron is shown in Fig. 5-27. :\1olecular orbital "'I
is of the bonding
type for cnch pair of carbon atoms, while 1f2 is bonding for the pairs 1- 2 and 3-4
of carbon atoms and antioonding for the pair 2-3. For t hat rcason the lotnl prob-.
ability distribution shows a dip at the center of the molecule. This means that the
strcngth of the bond betwccn the pair 2-3 of carbon atoms must be less than for
the pairs 1- 2 and 3-1. Experimentally the length of the bond 2-3 is 1.46 X 10- 10 m,
while bonds 1- 2 and 3-4 have a lcngth of 1.35 X 10- 10 m.
Our discussion can easily be gcncralized to includc a polyene or conjugate com-
]>ound consisting of a. carbon chain of 2/1 atoms; ill the classical valence modcl
this would be written as: . . - C-C-C-C-C- ... In addition to the u-bonds
betwccn pairs of adjacent carbon atoms, thcre are 2n "If-electrons s pread along the
molecule, as previously shown for butadiene in Fig. 5- 24 . There arc then 2n
closely spaced energy levels available, with ca])acity for 4n. electrons, to be filled
by the 27L "If-electrons. H ence when these molecules are in the ground statc only Fig. 5-28. Benzene molecular orbitals. (a) Localized IT-bonds; (b) unlocalizcd ... bonds.
the lower half of the energy levels arc occupied. Electronic motion in these mole-
cules can be excited by a relatively small amount of cnergy because of the ncarby in order to excite the electronic motion, the molecule must undergo a trallsition to
empty levcls. When there are 4n T-electrons, all energy levels arc occupied and, another electronic configuration; this requires much more energy. The avail-
ability of low-lying emllty energy levels is responsible for the fact that many of
these conjugate molecules absorb photolls in the visible regioll and therefore have
characteristic colors.
As a last example, we shall consider the cyclic conjugate molecule benzene,
CeHe. The carbon atoms arc located at the vertexes of a regular hexagon and
joined by u-bonds using sp: hybrid wave functions along each C-C line, as shown
c, c, in Fig. 5-28(a). The hydrogen ato ms are attached at t he remaining Sp2 orbital of
Fif!. 5-27. Totnl probnbility distribution of ,...-el ~ tron 8 in butadiene. each carbon atom. There arc also six 1T-clectrolls, one from each carbon atom, ill
 p

(5.7 5.7) Molecular rolalwlu 213

P. orbitals (the Z-axis is taken perpendicular to the plnne of the molecule) . These
r -dectrons nre free to move along the hexagon, constituting a sort of closed cur-
rent, as indicated in Fig. 5-28(b) . This account.s for the strong diamagnetism of
benzene and other cyclic conjugate molecules. The analysis of the wave func tions
and the energy levels of the "It-electrons is similar to that for butadiene, but the
fact t hat the carbon chain is closed introduces some new features with respect to
Fig. 5-29. Rota tion of a diatomic
molecule about its center of IlInsa. ____ ON.______
'
L
.. ________ oN,---Z.
open carbon chains, which we shall not discuss (see Problem 6.20).
We shall not pursue the s ubject of molecular structure any fu rther. This brief
diseussion of chemical binding is enough to illustrate the more fundam ental ideas ,
and to forewarn the studen t of the difficulties which arise when one attempts to due to the electrons, and therefore the moment or inertia of the molecule relative
use the classical conccpt of valency in too rigid a form . The formation of a mol- to the Zo n"i8 is zero. Thus the angular momentum of the molecule, for rotation
ecule is a many-part icle problem involving electromagnetic interactions, and thc around the Zo axis, is also zero and the total angula r momentum L of the molecule
problem must be solved according to the rules of quantum mechanics. is pcrpelldic.ular to the molecular a.""is. Given that ro is the equilibrium separatio n
of the nuclei and II- the reduced mass of t he molecule, the moment of inertia about
EXAMPLE 5.6. E&timate the first eKcitation cnergy of a lI"-electron in a conjugate an axis perpendicular to Zo and I>assing through the center of mass of the molecule
molecule. is 1 = II-r~. Wc may then write the kinetic energy of rotation of the molecule as
2
.50/11 1;0'" One can estimate the cxcitation energy of a lI"-electron by considering that "11"- E, = L / 2/. By virtue of the quantiZation of t he angulnr momentum we may
eleetrons move independently of each other and that their motion within the molecule write? :wc~ rding to Eq. (3. 15), 2 = h 2l(l + I), where l = 0, 1, 2,3, .. . , (that is,
resembles motion in a potential box (Section 2.5) whose dimension is of the ordcr of the a positive IIltcger). T herefore the kinet ic energy of rot.ation of the molecule becomes
Icngth of thc carbon chain. The wave functions would then correspond to the dashed
h'
lines in Fig. 5-25. If the carbon chlloin has 211. atoms, the re arc 211. ,..-elcctrons and the last
occupied electronic level corresponds to the nth level in Eq. (2.14). The energy differcnce
E, = 2ll(l + I) = Bhcl(l + 1), (5. 12)
between the nth and (n + I)th levels is the fiNlt excitation energy. Then
where it is customary to seth 2/ 21 = Bhe. The quantities h2/ 21 and B for several
22 2 222 22 ~o~ ccules are .given in Table 5-3, expressed in eV and in em-I, respectively. By
llE _"II" h (n+1) _ "II"II n. -~(2n. + 1) (5.11)
2m42 21'114': 21'114': ' glVlIlg s~ ~ccsslve values to l, we cun obtain the rotational energy levels of the mol-
ecule (FIg. 5-30). Successive energy levels, corresponding to I and l' = l I are +
where (I. is the length of the region in which the "II"-clectrol\S move, taken as the molecular separated by the amount '
length extended half a bond length on each end. For example, in the ease of butadicne,
with 4 about 5.6 X 10- 10 m and n _ 2, we get aT: - 5.86 eV, which coTre$lxmds to dE, = 2Bhc(l + 1). (5.13)
phowM of wavelength 2.12 X 10- 7 m. It has been observed that butadicne has strong
absorption for radiation of "Ilvelength 2.17 X 10- 1 m. Thus our crude model shows a
rehOllable agreement with the experiment. TABLE 5-3 ItOllltio"al and Vibra tional Conua nl8 of SomO'l Diatomic
Molfle ulell

5.7 ltlolf!culor lIoio.i lon. Molecule ,.,2/ 2/ , eV B _ fl / 4"11" / e Clll - I 1\"'0, eV vo, cm - I
Now that we have considered electronic motion in molecules which have fi"ed R, 8.0 X 10- 3 60.809 0.543 .395
nuclei, the next stcp in our analysis of molecular structure is to study nuclear mo- CI, 3. 1 X 10- 3 0.244 0.0698 565
tion. The simplest nuclear motion is that of rotation of the molecule around its N2 2.48 X IO -~ 2.010 0.292 2360
center of mass M if t he molecule were a rigid body. We shall first d iscuss the rot,, Li2 8.3 X IO -~ 0.673 0.0434 351
tion of d iatomic molecules. 0, 1.78 X 10--1 1.446 0.194 1580
WeelU) study the motion of a rigid body most easily by using a frame of reference CO 2.38 X 10- 4 1.931 0.268 2170
attached to the body and composed of the principal axes of inertia. hi the case of HF 2.48 X 10- 3 20.94 0.510 4138
d iatomic molecules (Fig. 5-29), the pri ncil>ai axes are the line joining t he two He l 1.31 X 10 - 3 10.59 0.369 2990
nuclei, N I and N 2 , or the Zo :lJ;is, and any line perpendicular to it through thc
HB t 1.05 X 10- 3 8.47 0.326 2650
Befo' 1.84 X 10- 4 1.488 0. 151 1266
center of mass. Becnuse thei r mass is so small, we can neglect the moment of inertia
 pi

'" (5.7
5.8) Mo/ecu/Ilr ribra/ion" 215

-----.----- , '", -- , ,--- "'"

Parity
,
5
~ ,r r
:~
, +
!
! -
"
Fig. 5-30.
of II.
Rotational energy states
diatomic molecule.
3---.~-----------
I
" o 20 40 ron so 100 120 140 100 1&1 -'1M) ",
__ 0 0_10 o
_00 0~'iO 3(.'
;, rm - '
,--rL----------- +
, .' ;g. 5-3 1. Rotational IIbsorption spectrum of HCI in the gaseous phase.
o +
possess a pcrmanent electric dipole moment. In the process of absorption of radia-
Because of the small value of .t,,2j 2l (_10- 4 eV) when compared with the trans- tion by tlle molecule, the permanent electric dipole moment interllCts with the
lational kinetic energy (which is of t.he order of kT - -k eV = 2.5 X 10- 2 eV at electric field of the incoming wave. In the l)rOCeSS of emission of radiation, the
room temperature), many molecules are found in excited rot ational s tates at room rotation of the dipole is responsible for the radiation. Therefore, homonuclear
temperature. Although the relative equilibrium population of the different rota~ diatomic molecules (which do not have a permanent electric dil)Ole) do not show
tional energy levels is an important problem, its analysis requires the use of pure rotation spectra. Figure 5--31 ilIuslrates the absorption rotation spectrum of
statistical methods, and we shall therefore defer it until Section 12.5. The wave HCI in the ga.s phase. Each dip cOl'responds to a m:~ximUIll or rcsonant absorption.
fUllctions corresponding to the rotational motion are the Y'm(CO, cf introduced in We can see that, in agreement with the theory, as given by Eq. (5. 15), the fre-
Section 3.5, and the angles (/I, <1 define t.he direction of the molecular axis Zo rel- quencies are evenly spaced.
ative to the coordinate axes X , Y, Z, fixed in the laboratory. Hence the parity Equation (5.12) holds for the ea.se of a rigid molecule. However, whcn the
of each level is (_ 1)1, and thus succcssive energy levels have opposite parity, rotational energy increa.ses, there is a stretching of the molecule due to a cen trif-
since they are similar to the s-, p-, d-, atomic orbitals. For electric dipole ugal effect; this z'csults in an increase in the moment of inertia and a correction to
radiation, the allowed transitions are those for which Eq . (5.12) is required. Our disc\\ssion appl ies nlso to the rotational spectra of
linear molecules such as COlor !'I CN. Those molecules- which, in general, have
t.l = i , (5.14) relatively larger moments of inertia- have much closer rotational energy levels
than most diatomic molecules, and correspondingly lower frequencies in the rota-
a selection rule similar to that found in the atomic case. Thus the only transitions tional spectrum.
possible are those between adjacent levels. Some of the transitions, eorrcsponding
to absorption, are indicated in Fig. 5--30. When we use Dohr's rule, B2 - E\ = hI',
the fn."Quency of the radiation emitted or absorbed ill a rotational transition is 1i.1I ~11)/f'c lllllr V i/,rlltifl"S

I' = t.B/h = 2Bc(l + I) 0' ji = 28(l+ I), (5.15) So far we have considered the nuclei as fixed rebt,ive to each other; however, the
shape of the potential energy curve for a diatomic molecule (8uch as those shown
where l refe rs to the angular momentum of the lowest level involved in the transi- in Figs. 5--6, 5-13, and 5-1 4) suggests th nL the nuclei in a molecule are in relative
v
tions and is lhe wave number expressed in cm - I . T hus the rotational spectrum OSCillatory motion.
of diatomic molecules (;onsists of a series of lines l.."Qually spaced an amount Let us consider a diatomic molecule whi ch hilS n potential energy for a given
electronic configuration, as shown in Fig. 5--32, where ro is the equilibrium sep!l.ra-
t.V= 28 em -I . tion. Given that the nuclear motion corresponds to an energy H, the two nuclei
oscillate so that, classically, their separation varies between Oa and Ob. The
By measuring t.v, we call compute 8 and thus the moment of inertia, and from it ~otion of the nuelei must , however, be described according to (juanlum mechan-
estimate the IHlciear separatioll TO' ICS. If the potential encrgy wcre that, of a simple harmonic oscillator, represented
Pure rotational speetra fall in the microwave or far-infrared regions of the spec- by the !laraboia t.l.:(r - '0)2, the rclntive oscillatory motion of the two nuclei
trum. fn addition, for a molecule to exhibit a pure rotational spectrum, it must Would be simple harmonic, and the results of Sectioll 2.u wou ld be applic:lble.
 p

216 Afoltwlt. (5.S 5.S) Mol~culllr ribrllfiofl.' 2/7

for several diatomic molecules. The vibrational frequencies of most diatomic

molecules fall in the infrared region of the ~I>ectrum. For a vibrational transition
e, to occur, either in emission or absorption, the diatomic molecule must have a
permanent electric dipole moment. Thus homonuclear molecules such as H2 or
N 2 do not show pure vibrational transitions, since they have no permanent clectric
Fig. 5-32. Electronic potential energy in dipole moments and they do not exhibit. an infrared spectrum. Bllt polar molecules,
a diatomic molecule.
such as HGl, show strong vibrational transitions.
T he molecular energy due to both rotation and vibration can be expressed by
combining Eqs. (5.1 2) and (5.16), so that we have
---1-1--------------------- h'
E = E .+ E. = (~+ t)hw o + l (t+ 1). (5. 18)
2f
D,
In generfll, t.he quantity h2/ 2f is much smaller (_ 10- 4 eV) than hwo (_10- 1 eV),
..1
,,,8 B and we may.say that, to each vibrational level, there correspond several rotational
, levels, as shown in Fig. 5-33. When the selection rules tou = 1 and tol = I
~ "': O (vibrational ground 8tn:) are taken into account for a transition between two rotational levels belonging to
two adjacent vibrational levels, the rotation-vibration spectrum results. T his

,
D
'.
The angular frequency of the 08cillatiolls is "'0 = ~, where I-' is the reduced
mnss of the molecule. In Section 2.6 it was shown that the energy of the oscillatory
motion is quantized IUld givcn by Eq. (2.21). Hence the vibrational energy levels , - - - - - -
of a diatomic molecule are e:>.:prcssed appro:>.: imately by

B. = (v + ,)lIwo, (5.16)
3 -_ _ _ __

where V"" 0, 1,2,3, . . . (positive integer). Therefore the vibrational energy levels
.1I - - J .11 _ +1
of the molecule are C<lunlly spaced an amount Awo and the molecule has a zer(r
poiltl vibrational energy equal to lhwo. Beeause of the zero-point energy, the dis- 2 _ _ _ _ __
sociation energy of a diatomic molecule is D. = D ~ thwo, as may be inferred I
from Fig. 5-32. The selection rule for electric dipole transitions among vibrational

~n-o
levels is the snme lUI F.q. (2.34); that is,

fl.ll _ l. (5.17)

Since the only allowed change of II is to a neighboring energy level, the only fre-
quency absorbed or emitted in a vibrational Lrnnsition is equal to the natural 0_
, I I I I I : II II I
clnssiCilI frequency 1'0 = wo/ 2rr. T able &--3 gives the values of Ilwo and j;o = lIol c
--- ____I ...
.1. ____ _ _ _ I'brunch
/(brnnch
4/ - - 1 .l1 _ + 1
Thi~ ~clcct ion rule is not rigorous because the potential energy, 11.8 shown in Fig. 5-32,
is not that of a harmonic OI!cillator, and higher values of tou are alw possible, although less Fig. 5-33. Vibrational and rotntionnl Fig. ,,...31. Vibration-rotation tran$itions
]lrobable. energy le\'els of a diatomic molecule. in a dintomic molecule.
 ""
218 fl,foiecukf
(5.8 lUole1:u/ar ~ibralifHlt 219
5~)

Fig. a-36. Normal vib rations 0/ poly-

atomic molecules. (a) C02:""1 - 1337 em -I,
1012 - 667 cm-I, ""3 - 234!l em- I; (b) H20:
WI - 3657 em-I, 1012 - 1595 cm- I, 1013 -
3756cm- l .

I R-Imo.nch (.J

I-
"-l>r~nch

o
o
2700
JOOO
Wa\'e number, cm- l
Vibration- rotation ab80rlltion Speetrum of He!.
,"' jg. ;'>-3:>. The major dip!! are due
., ~

to HUe! Bnd the l!ms ller dips are due to J{37CI.
consists of lilies whose frequencies nrc given by
V.,, = "0 2Bc{t + I )
0'
V. = Vo 2/J(l + I), l = 0, 1, 2, .. _J (5.19)
where l refers to the lower rotutionnl 10\'01 and B is a.s defined in Section 5.7. The
frequencies urc equally spaced nn amount 2Bc on both sidcs of the central frequency
"0- The line of frequen cy "0 is missing from the spectrum bec:lUse it requires n
lrallsition with tJ.l = 0, which is forbidden. F igure 5-34 illustrates the possible
rotll.lionnl transitions for the vibrational transitions 11 = I ...... II = O. Those lines
with tal = + 1 arc called the Rbrnnch of the spectrum ; the name P-branch is
used to designate those lilies with l!.l = - I. The intensities of the d ifferent transi-
tiolls for emission alld absoq>tion depend on the population of the initial energy
level, which in turn depends on t he temperature of the s ubstance. We shall con-
sider this subject in Section 12.5.
The rotation-vibration spc<:trum of HCI is shown in F ig. 5--35. Because both 1'0
and (depend on the mass of the molecule, the spectra of molecules having dif-
ferent isotopes, such as H 3~C l and !t Hel, arc slightly displaced. This is clearly
rcr:ognizable in the figure.
(bJ
Our theory can be refined in the following way. The potential energy curve of
Fig. 5-32 does not correspond to that of a simple harmonic oscillator IUld the
oscillations are anharmonic. This requires additional terms in Eq. (5. 18) to prop-
erly describe the vibrational energy. In addition, due w the shape of the potential
energy curve, the equilibrium separat.ion of the nuclei changcs n.s the vibrational
energy changes. This results in u. change of the moment of inertia, and hence of
the rotational energy. This is u. vibration- rotation interaction eITect. All these
corrective terms arc usually obtained empirically by analyzing the spectrum of
the molecule.
The vibrational spectra of polyawmic molecules arc morc complex. T hese
spectra are analyzed in tcrms of the nbrmal modes of vibration of thc molecule,
which arc vibrations in which all nuclei vibrate with constant phase relations. To
each normal mode there corresponds, in general, a different frequ ency of vibra-
tion. Howevcr, symmetry may make some of the frequ encies C(lual or degenerate.
lo'igure 5-36 shows the normal vibmtions of two simple molecules : Carbon dioxide,
CO2, is a linear molecule and H 2 0 is n pIlUlar molecule. For a frequency to be
ac tive in the vibrational or infrared spectrum, the corresponding normal vibration
must induce an oscillating eleclric dil)(}le in the molecule. For example, COllsider
the Symmetric CO 2 molecule, which has no permanent electric dipole moment.
Oscillation "'I preserves the symmetry of the molecule and does not induce an
electric dipole moment; t herefore the vibrational mode is spectroscopically inactive.
 -
220 Molectlltl
(5.8 5.8) Molecular ~ibralionl 221
1~, iXItI

--Intennediate
or virtll"1 ~t.~te
11 ,000

...
'
(Ji)))liiOO

3-+-+-
... ( 111 )~eoo!
,-+-t--
... (210)--~
(03I) _~H
( 130)-8V~

o-;:,_=,_:::;O_".C
--'--f--Initial
sta te
....U<nd -.+
Ibyit!igh ,\nti-8tokCll
ll<::Itlering ,
Hllman ilCMtering

Fig. 5-38. Hl1yleigh and Raman lICl1ttering.

though it is esscntially a scaltering process. SUPl}Qse tklt we illuminate a gas

sample with monochromatic radil\lion of frequcncy v. H we observe the radiatio n
scattered in a di roctioll at right !Ingles to that of incidence, we find that the radia-
(lOO)"'Jii7
(O'JO)_
Jr~r
".
(001)_ tion contaills, in additiOIl to the frequency" equal to thnt of the primary or illcident
mdiation, which is the CQlwrent or Rayleigh IICallering, radiation of frequency v v.
(where ". corresponds to a frequency of the vibrational sl>cctrum of the molecule).
T his is o3.lIed /laman scattering. We can interpret Raman scattering in the following

..
manlier : suppose that a molecule is initially in the vibro.tionaJ stllte v (F ig. 5-38).
(0101 _ _ When t he molecule absorbs radilltiOIl of frequency v, it may go to all excited state.
'm
, If the e.xcited state is not a st3.tiollary olle, thcre is an immediate re-radiation of the
absorbed energy. The molecule may return to the initial s late, emitting radiation
of t he same frequency as the incident light ; this is Ray leigh scattering. The mol-
-,
" ..... ttule may also return to another vibrational level which, due to the selection rule
il~ = I , mus t be olle immediately above or below the initial level; this is Raman
!!eattcring. Thus the emitted radiation has a frequency y + ".
or " - Yo. The
line of frequency" - ". is called the Stoke8 line and that of frC<llLclley v the + ".
anti-Slokee line. The Ramall effect has also been observed in the rotational spec-
On the other hand ""3 induces a di I trum. In this ease the selection rule is ill = 0, 2.
and "'2 " dipole m~ment IJCrpcndicr::;a~ ~~O~~lent ~ara][el to !.he axis of t he molecule
are active spectroscopically I ncide t i l e , aXIs of t he molecule; therefore both EXAM /'U; 5. 7. Rclation between the constante in the :>.Ioroo pote ntial (Example 5.3)
of the mode shown plus on~ in whic~ ~I:~:~: dO~bly degellern~c, since it consists 8nd the vibrational frequency of a diatomic molecule.
A polyatomic molecule lhcrcfore hM 8tlvera,OSClllate ~rpc~dlcular to the page. Solution : Given that 1-:, _ D(I - e- f .......J)', we may use the CXIJression
Some arc illustrated in Fig. 5-37 for H 0 Each~~ of vlbrutlO~ar cnc~gy levels.
corresponding rotational lev,l, th, b 2 "k" I these levels IS assocmtcd with
. , ra y ma 'mg t Ie s ........ t (I
analyslll of rotation.vibration "peet .I I ...-:- ra rn ler complex. An
and retain only the lirst three tcrms, an approximation which ie \'alid \... hen :z; is email.
ular dimensions geometry di Q:~~' tr~ proVI( C8 va uable mformation about molee-.
. . ' , """" HI. lOll energy and SO 011 Setting:z; _ a(T - TO), we have tha t
1\ II Irlterestlrlg process !Jed I R ' .
C, V. Raman (1888- ')~ I t Ie amall effcct-.after the I ndian physicist /0.:, .. D[a(r - TO) - ;a'l(T - ro)2 + .. f
s re ated to molecular vibrations and rotations, al.
_.Da 2 (r _ ro)2 _ Di(r _ ro)3 + ... (5.20)
 222 (5.9 5.9) 223

.If the oscilllUi~ns were harmonic we should have E. - it(r - roP. Thus the first ternl To a given electronic stale there correspond many vibration!!! slates and to each
In Eq. (5.20) IS the harmonic potential energy, and we may write it _ D(l2. Sin~ vibrational state there correspond several roOtational states, As II first appro . . ima-
ColO - ...!fji., we then have
tion, we may write the energy of the molccule in the form
fl _ J.C~/2D,
which gil'es th.c eonsta~t (I in terms of known moleCular constants. The second term i8 E = Ee+ E.+E, = E. + (11+ ;)"CoIo +:;I(I+ I), (5.2 1)
the anharm.onlC 1l'01~nt,al energy and contributes additional lernUl to the vibrational
e~er~, as gll'en by F..q. (5.16). For example, it can be shol\'n that, to the fiNlt order, the where E. refers to the electronic energy at the minimun oOf the I)()tentia! energy
\'lbtatlonal energy can be written in the form curve (see Fig. 5-39). In an electronic transition all three energies may change.
T he frequency Wo lind the moment of inertia I are, in gNleral, different foOr both
1::. - (11+ ;)h"'O - (v+ i)2z.hwo electronic states. Therefore we must write the energy change in the electronic
where 7. - hColo/ 4.D. transition as
11t:= 8" - E' = I1E. + I1E. + 118.
:;.9 ""If,tronlc Tr"n~ition~ in .4'olecul,!~
where t.b'. = t.'~' - 8~ is the change in electronic energy, given by the energy dif-
A given mo.lccule may havo scvera! electronic configurations or stationary SlalCll. ferellee of the minimum oOf the two electronic statcs,
L()t us consnier, for sim l)licity,:I. diatomic mo!ecule; to each electronic stlllo there
corl"csponds It I)()tential crl()rgy similar to tho electronic states of H + shown in I1B. = E': - E ~ = (v" + ~)hwO' - (v' + ;)'!W~
~ig. 5-? The two. nuclei in the excited electronic statcs have, in gcne~al, equilib-
Tlum d.lstanecs willeh IIro different from the olle for the ground state. Two such is the ehangc in vibrntional energy, and
potenl1?1 energy curves nrc shown in Fig. 5-39. The separation of these energy
CUtv.cs IS ofYlC o~der ~f I to 10 eV. Thus when a molecule c:..:perienccg an elec- I1E, = E;' - E; = ;~~, l"(l" + 1) h
- 2 ;, l'(l' + I)
t~Olll.C tranSition, Jumplllg from one electronic configuration to another th .. radia.-
tion lI\volvcd falls in the visible or the ultraviolet regions of the speclr~m. is the change ill rotational energy. The terms with double primes correspond to
the state oOf higher electronic energy and those with single primes to tllC state of
lower electronic energy. The frequency oOf the radiation emitted or absorbed in
an clectronic transition is therefore the sum of three terms,

l{ol.,tional
Higher eletlronie
~tllte. "..;
I1E =
v= h V. T ".("
V ,v') + v,"
(I" I')
lev"", E;' __- - -
where ". = I1E./ h is due to the change in electronic ellergy, and ".{v", v') and
v.(1", I') coOrrespond to the changes in vibrational and rotational energies, respec-
tivcly. The frequen cy v. is the largest. FoOr a given electronic transition the
Spectra consist of a series of band.! ; each band corresponds to a given value of v"
and v' and nil the possible values of l" lind I'.
To determine the possible values of (v", v') and (l", l') we nccd selection rules.
I.o"cr ck-ctromc When we consider electric dipole transitions, the roOtlltional selection rule is
81a1C, 1
111= O,I, nol" = O .... I' = O.
Note that 111 = 0 is 110\\' allowed because there is a chllnge in e::onfigurntion of the
molecule during the transition and parity considerations do not enter in in the
Slime way as in previous eascs. HoOwever, the:: transition I' = 0 .... l" = 0 is for-
bidden because, if it were allowed, it would then bo iml>ossible to satisfy thc prin-
ciple of conservation of lIngulftT momentum, since t he radiation emiW..'<i or absorbed
Fi g. 5-39. VibratiOnlll and rotational energy len18 associated with 1"'0 electronic st!ltCii. carricg OIlC unit of lIngular momentum.
 Mol ulu COIl(/lUion
'" Another selection rule is t.hat the spin of the molceule must be the same in both
(5.9 5.10)

electronic states involved in the transition; that. is, AS = O. This rule is due to
the fact that. the spin..<Jcpendcnt forces involved in the transition arc lIot strong
enough to alter the coupling of the electrons' spin ; however, this selection rule is
not rigorously followed.
The vibrRtional selection rule is somewhat more involved. Note that lUI elec-
tronic trnllsilion occurs ill a time of the order of 10- 16 8, while the nuclear oscilla-
tory motion hag a period of about 10- 13 S, or onc thousand times longer. There- ----------------
fore, during the electronic transition, the nuclear separation remaill! l'SSCntially
, C"
the same. This means that a [inc joilling the initial and final positions of the
nucleus in Fig. 5-39 at. the time of the transition must be vertica\. On the other ,
2 ,"
hand , the most f:womble transitiOlls must be those for which it is easiest to quickly
adjust the /luclear motion to the new electronic conditions. In terms of classical o
mechanics, the most favorable vibrational transitions should occur when the rela.--
tive nuclear velocity is the same in both states at the time of the tmnsition. Since
the nuclear velocity is zero at the ends of the classical osciilation, lhe most probable
, 1 ------------
/ra1l8iti0118 occur whell, allhe time of trallrilion, lhe nuclei are at olle C1u1 of their olJCi(.. C'
lation and at ihe 8ame il!lernuclear distance for both the initial olm final 8tale8. In
the lnngunge of (Iuunlurn mccilanics, we could say that the most probable transi-
tions arc those for which the vibrational wave function suITers the leMt distortion
at the time of the transition. Since the oscillatory wave functions nrc very similar o
at tile clllSSical ends of oscillation (remember Fig. 2~19), we reach the same con-
clusion with the quantum-mcchanical model as we do with the classic:lJ model. o
Let us refcr to Fig. 5-40, for examplc, and suppose Ulat a molecule initinlly in
the vibrational state v' = 5 of electronic state C' suffers an absorption transition Fig. 5--10. Electronic tlll.nsilions &110"00 by the Franck-Condon principle.
up to electrollie stale C". The most probable final vibrational states are obtained
by drawing vertical lines a alld b at the ends of the classical oscillation and extend- ;";.ItJ {.ondus;on
ing them UI) to intersect eurveC". Line a falls near II' = I, resulting in a transition
II = 5 --+ II' = I. Line b falls above the dissociation ellergy and would result in In our discussion of molecular structure we have considered only the most. im-
the dissociation of the molecule. When the transition involves the lowest vibra portant aspects. There arc many details that we have not mentioned. For example,
tional state (II or 1''' = 0), the vertical line should be drawn through the center of nuclear spins have an influence on molecular energy levels. I II the simplest mol-
the oscillations, as in c and d, resuiling (in our example) in the trallsitiOIl ecules, Hi and H 2 , the two protons may have their spins parallel or alltiparailel,
resulting in orthohydrogen and parahydrogen.
11= 0--+11'=4 Molcculur symmetry plays a very important role ill determining the possible
normal yibrations as well as the allowed transitions; however, a discussion of
v' = 2--+ II' = O. molecular symmetry is beyond the level of this book.
The reaso n for this is that the maximum of the wave fU/lction for the ground In the case of polyatomie molecules the spec~ra may be so complex that it may
state of an oscillator OCCUI"8 at the center (sec Fig. 2-19). We have considered be impossible to classify tJlCm NS we have done in Section 5.9 for the spectra of
absorption transitions; the same logic applics to emission transitions. Therefore diatomh.: molecules. However, this complexity scrves a useful ])Urpose, in that it
vibrational transitions associated with electronic transitions do not. comply with permits us to identify a given compound by observing its spectrum. On the other
the selectioll rule 61' = I and I' muy suffer a change of several units. hand, certain atomic groups exhibit wcll-defined electronic tlnd vibrational spectra.
The rule we have explained for determining the yibrational transition ill all Observation of the corresponding fn.'qllencies serves M an indication of the presence
electronic transition is known as the FrallCkCoMon principle. It \\1M formulated of such groups in a molecule.
first in clllSSical terms by James l~rallck alld reformulated according to Quantum We may conclude by saying that one of the most ]>owerful tools for determining
mechanics by li:dward U. Condon nbout 1926. molecular structure is the tlnalysis of molcculnr spectra.
 226 Mom:ulu '1'11

IIf'/~"enf"f'fI is less than twice the dissociation energy of given by

lit (61.06 kcal mole-I). '. _ -,.'e2/ (4 .. tor) + be-a.3xlol..,
1. ~ Thc Forl'e Between :\Ioleeulc~,~ B. Derjaguin, Sci. AnI., July 1900, page 47 5.5 Explain why the ion 11 2 is leM stable
than lhe ion Jlet if both have the same where ~ is the charge 01 the ions lind b is
2. ~SOIllC .\spec\..;! of Molecular Physics," J. Lew'lt, .I m. J. PltY3. 28, 192 (1960)
eleetronie configuration. Which ion ~hould a cons tant determined from c.xperimental
3. "Chemistry of the Noble Casc.~," II. Selig, J. :\ill.lm,tI' nd II. ClaM:!('lI, &i. .Im" :\Iay ha ve the lll.tger internuclear separation ? valucs for the dissociation energy. I."iud b
1964, page 66
5.6 Fiud the energy of Li2 relative to the for KCI, given that the equilibrium dis-
'I. "The Zeeman Effect in ;o.lolcculcs," C. Quade, .I m. J. Phy" 32. 634 (HI64) system 2Li++ 2e, with all four particles tance for this molecule is 2.79 X 10- 10 m.
a. Th~ &~ntifie I\ndeat'Or. l'cw York: Rockefeller Institute Press, 1965; ~The ,\rcilit.ec- at infinite separlllion. The ionillltion Plot the potential energy. Find the dis-
ture of ,\!olecu]es," by I., Pauling energy of lithium is 5.39 eV. Calculate !$OCiation energy of KCI into K+ and CI-.

6. Silmmetr" in Chemi$lrll, P. I)orain. Heading, :\IJI.lI,;I.; ,\ddison-WCillcy, 1965 the coulomb repulsion energy of the Li+ Calculate the energy ree.uired for it.'! dis-
7. Th~ Siruc/",'eoj .Ifo/teu/e,. O. Barrow. XCI'.' York: Benjamin, 1964 . iOlls a~ the equilibrium selltlration, 2.67 A. sociation into neutrall)roducts.
Then compute the energy of the two val 5.13 A fairly precise empirical expression
8. f.'/tdror" and IhtCcLoaftnl Bond, II. Gray. !\ew York; Benjamin, 1965 ence ele<:trons. for calculating the potential energy of two
9. I!:ltmt1l" of JrQ~'e .l/uhaniu, K. ;\ioll. Cambridge, England: Camhridge University 5.7 Discuss lhe electronie configuration ions in an ionic bond is
Press, 1962, Chapter 5, SectionIl2,3, 3, -1.2, 4.3, 4A, 4.5, alld 4.6 and bond st ru cture of (a) Ab, (b) S2, IlIId
10. Structure of .UaUer, \\;. Finkelnbu, g. New York: Acadcmic J'rc83, 1964, Chapter 4, (e) Ch, Write, in each callC, the symbol for
Section 7; Chapter 6 the grou nd-state term. where v is the chnrge of the ions and a,
II. QUalltum T heory of .1fl!/ler, J. Slater. I'\ew York: l\lcGraw-lIi\l, 1951, Chapters 8 5.S Given the molecule NO, discuss its b, and d are constan ts obtained experi-
IIml 9 electronic configuration and bond struc- mentally, For LiF the constanl$ are: a -
12. Elemenlorll Introduction/I) J/oIuu!"r Sp/ra, 1J. Bak . Ncw York: intcrscicnce , 1960 ture. Compare wilh the N2 molecule and 3.25A-t,b _ 895eV,andd _ 2.68eV A6.
state. Det:ide which molecule is more Determ ine the energy required to disso-
13. Chemical Bindillg ""d Structure, J. Spice. Ne"' York : "Iacmitlan, Hl64 8table. ciate a !.iF moleeule into its two ions. (The
14. Wal"e Jfuhanicf and r"lency, J. Linnett. London: Methuen, 1960 5.9 Write lhe electronic configurations for bond length of LiF is 1.54 A.) Also com-
15. T~Chemical Bond, third edition, L. Pauling. Ithaca, N.Y.: Cornell [nil'ersity Press, ~he following heteronuclear diatomic mol- pute the euergy required for dis&lcialion
1967 ceules: (a) LiH, (b) CN, (e) SO, (d) CIF, into two neutral atoms. The ioni~ation
and (e) III . Determine whether the mol- potential of lithi um is 6.39 eV and the
ceulCll are polar alld, in the affirmative ell!lC, electron affinity of Hnorine is 3.45 eV.
'r"I,I,."'II identify which end of the molC<lule is 5.14 Show that the wave fun ction
positive and which end is negative.
5.1 The ground-state cnergy of Ht l'cl'l- 5.2 Calculate the cOlltribu tiou of the
6.10 Calculate the energy released when of - N(s+ap.+"Jlw+l'p.)
live to the system comlXlSed of hydrogen coulomb repul~ion of the two nudci to the
in itll ground st!!.te and H + at infinite IICp- AICI and AllJr dissodate into neutral
energy of Hi in its ground ~tate. Compute has its maximum along the direction of the
aralion is -2.65 eV. Comllute: (a) the atoms. The equilibrium separations for
the energy due to the interaction of lhe vector a - II .a + .. ,ft + " ,"Y, and its
energy of IIi relative to the eystem electron "ith the lIudei. [/lint: UIIC the these molecules are 2.13,\ and 2.30 A,
minimum in the OI)I)05ite direction. Hence
res.peethely. The respeetive experimental
data of the prettding llroblcm and recall two hybrid wa\'e functions corresponding
H ++H++e valuCl! are 71.5 kcal mole-I and 65.3 kcal
that the equilibrium IICllaration of nuclei to vectors a and a' ha\'e their maximum in
in lit is 1.06,i..] mole-I. Illint: See Examl)le 5.5 for a sim-
at infinite selltlrationj (b) the energy of the directions making the same angle as a and
ilar calculation for NaC!.)
system Ht + e at infinite separation rela- 5.3 DiSllOCilllion snd ionization energies a'. Write the vector a for each of the Sp3
tive to the system H + II , again at infinite are frequently expressed in kcal mole-I. 5. 11 When a hydrogen atom eaj)\ures an and sp~ hybrid wave functions introduced
separation, and with both atoms in thcir Show that one kcal mole-I is eqmd to electron to become H-, an euergy equal to in Section 5.5. Show that in the Sp3 case
ground Slates; (c) the ioniution energy of 4.338 X 10- 2 eV. Expresslhe di!l8OOiation 0.. 49 eV is released. The ionization ellergy the vectors point toward the vertexes 01 a
Ih if the dissociation energy of this mol- energy of H2 in kcal mole-I. of lithiulII is 5.39 eV. Compute the dis- tetrahedron, making angles of 10ge 28', and
ecule into two hydrogen atoms in their SOCiation energy of Lill, given that the in the Sp2 CMe they are ill lhe Xl'-plllne,
5.4 ~xplll.in why the bond length of Ht is
ground states is 4A 8 eV. Compare the nu clenr equilibrium separation is 1,00 A. making anglCll of 120. [llint: Note that
1.06 '\ , while II, ha~ a ahorter bond length
result in (e) wilh the ionintion energy of equal to. 0.74 t\l.i() explain why the dis- 5.12 Au acceptable empirical expression lhe vector lI,p, + " ~I). + II ,P. is prOI)() r-
alomie hydrogen. sociation energy of Ih ( 103.2 kcal mole-I) for the potential energy in ionic bonding is tiollal to c.1
228 Moin:ul~,
5.15 Show t.hat. the four Splhybrid wave
fun ctions are orthogonal. Repeat for the
8111 WS\'C fU!lclions.
5.16 Discuss the bond 8tructure in
(a l ClHs, (b) CaH" and (e) C3 n~ .
5.17 Analyze the bond structure of the
following molecules: Ca) C02, (b) CS2,
(el CSTe, (d) Cl, (I'll CdC!" (r, OCh,
(g) ONCI, (h) Snel2, (i) si-, and
(j) CN~-. Indicate wh ich molecules are
linear and which are bent.
5.1 8 Analyze t he bond structure of the
following molecules: (a) A ~ H 3, (b) SbF3.
(el I30~ - , (d) OHt, (I'll PCI3, (f) Seof-,
(g) Br03, (h) SiF ~ , and (i) pr3. Indicate
which molecules a re planar and which are
pyramidal.
5.19 AnalYlc the bond structure of BHa
and DI" ~, indicating whether the mol-
ecules a re planar or [lyramidal.
5.20 DillcUM the H 20 and N H3 mol-
ecules, ulling 8J)3.hyb ridized wave fune-
t:ons for the oxygi)n and the nitrogen
at.oms, li!!llleetively. I)Q you think that
th is is a better de&eriplion of these mol-
ec ules than the one presented in the text?
5.21 Analyse the bond st ru cture of C Hi"
snd H30+.
5.22 DiseulSS the bond stru cture of the
moleeule IhCO. 18 the molecule planar!
5.23 The eleetri c dilKlle moment of H20
is 6.2 X 10 - 30 In C. Find the dilKlie mo-
ment oorreslKlnding to each o-H bond.
Gi"en that the bond length of o-n is
0.958 A, what fraetion of the hydrogen
eleetron has bee n transferred to the oxy-
gen atom?
5.24 l'he effective totailength of the con-
jugate molecule CH3-(C1I-C H-)tC H3
is 9.8 A. Plot the energy levels occupied
by the .-electrons. Find the energy and
wavelength of the phot.ons absorbed when
one of the uppennost .-electrons is exci ted.
5.25 The ,B-carotene molecule is a conju-
gated molecule having 22 :If-electrons. I t
has been found that this mo[eeul e shows
strong absorption of radi ation at 4510 A.
Estimate the total length of the molecule.
5.26 Show thst the moment of inertia of
a diatomic molecule about an axis llerpen-
dieu[ar to the line of nuclei and Pll88ing
through th e center of malSS is I - "ro,
where " is the reduced m&!l!l of the mol-
ecule and,o is the internuclea r dis tance.
5.27 The adjacent line., in the pure rota-
tional spectrum of 3~CII'Jo' are 8C1>arated
by a frequeney of 1.12 X ]0 10 Hi. What
is the in teratomic distance of this moleeule?
5.28 (a) Caleulate the energy and wa,'e_
length of the photon ab1!Orbed when a
2ooHg35Cl moleeule ('0 _ 2.23 A) makes
the rotational transitions I _ 0 - 0 I _ 1
and I - I ..... l _ 2. (b) In what region of
the electromagnetic spect rum are theso
lines found ?
5.29 Suwose tha t the equilibrium !!Cp-
aralion in the H 3~C l and H37CI moleeules
is the same and equal to 1.27 .1.. Compute
for each molecule (a) the constant B for
the rotational levels, (b) the energy of the
first two excited rotational le ~ 18 , (e) the
frequeneics and wavelengths correspond-
ing w the trallllitions 1 _ 0 __ I _ I and
I - I -+ l _ 2, and (d) the frequen cy
difference for suecessive linea. Comlmre
your rcsul(3 with Fig. 5-31.
5.30 Compute the energy of the first three
excited rotational states in CO and CO2.
Determine the wavelength of the photons
absorbed in tran~it i on s among such energy
le\e[s.
5.31 The rotational energy levels of a
molecule having two equal principal mo-
ments of inertia are given by
, I 2+ 21('12 - I7') I.'..
E..,. - 21, 1~
where II corresponds to llxes X and }' find
12 eorresponds t.o tIle Z-axis, and
{,' - ""1.
Using this equation, estimate t he relative
posit ion of the rotational energy levels of
a molecule having (a) 12 - 0.81" (b) 1~ -
1.21 1. Plot the le\'els as multiples of
11 2/ 2/ 1.
5.32 i\ dia tomic molecule i~ not rigorously
rigid and, due to a centrifugal eflect, the
intemudear distance inerellllC!!!\.lI the angu-
lar momentum of the moleeules increll!lCs.
(a) How should this moleeular stretehing
affeet the energy le\'els, in eoml>arison
with the values given by Eq. (5. 12)1
(h) An empirical expression for the rOla-
tional energy is
where 6 i~ the stretching con ~ tallt. Obtllin
expression for the frequencies due to
I\.Il
transitions among rotationallel'els. Com-
pare with Eq. (5.[5) and see if the stretch-
ing effect is recogni~able in Fig. 5-31.
., .,
Fig. 5-.11
5.33 Two bodies of masses 1111 and m2,
respeelil'ely, are joined by a spring "'ith an
el&:ltie constant k (Fig. 5-41). Show thM
if the Sllring is atretehed and ",le&!!Cd the
mas.;;oes will ~iIlue with a fre<lueney
~ _ (1/ 2T) V'k7P, where ,.. is the reduced
mass of the system.
5.34 Caleulate the energy of the three
lowest vibrationalle"els in HF, given that
,,.
the force constant ill 9.7 X 102 N m- 1 .
Find the wave nu mber of the radiation
ab1!Orbed in the transition P - 0 -+ 11 - 1.
5.35 The infrared !!])(!(l lrum of CO, at low
resolution, shows an ab1!OTI)tion band ren-
tered at 2170cm - l Find the force con-
stan t in CO. Plot, to seale, the potential
ene rgy eur\'e.
5.36 Calculate the ratio of the \'ibra-
tional frequencies of IH3SCI and 2n u CI
molec ules, assuming that the force con-
gtant is the same for both moleeules.
5.37 Wha~ is the force constant for the
lI e l moleeule, given tha ~ the vibrational
frequency is 9 X 10 13 lh ~ Also find the
!cro-1Klint energy.
5.38 Find the vibrational freque ncies of
liD and D2, givell that the 112 molecule
absorbs infrared radiation of wavelength
2.3 X 10 - 6 m COrrtSIKlnding to I\. vibra-
tional trnMi~ion with /lv - I and no
change in rot/l.lional or electronic energies.
Assu me the IIILme force constant for the
three mol ecule~. Compare wilh the experi-
mental Va11l1:8.
5.39 The three \'i brational frequencies of
C02 art 667.3 em - I, 1388.4 cm- I. and
23~ 9.4 em - I. Make a sketeh of the first
few \'ibrAtional energy levels of this
molecule.
5.40 The moleeule CO h&:l an eleetronie
tran~itiop thst I)rorluces IICveral bands in
the viSible region (around 6000 A). Esti-
mate the separation Ilmong adjacent
rotational linea in eaeh band. Do you
eXlleet the band to al)pear eontinuous in
a low-resolution speetroscolJe?

6 6.2)
SOLIDS
6.1 Jnlroduclion
6.2 Types of Solids
6.3 Band Theory oj Solids
6.4 Free-Elecl'ton Model oj a Solid
6.5 Electron Molion in a Periodic Slruclttre
6.6 Conductors, I nsulaiors, and Semiconduclors
6.7 Quantum Theory of Electrical Conduclivily
6.8 Radialh'e Transitions ill Solids
'""
,
Typu of wlids 2JI
6 . 1 Introduction
Matter in bulk , in the way it. affecL!! our senses, is 9.11 aggregate of a very large
number of atoms. Grossly speak ing, these aggregates appear to be in th ree physical
states or phases: gases, li<IUids, and solids. In gases t he average distance between
m oleculc~ is much greater than the size of the molecules and the intermolecul.ar
forces are much we.ker than the forcCi! which hold the atoms ill the molecule
together. Thus in gases the molecules retai n their individuality. At t he other
extreme, in a solid , the atoms (or molecules) are tightly packed and held ill more
or less fixed positions by forces, of electromagnetic origin, which are of the same
order of magnitude as those involved in molecular binding. Thus the shnpe and
volume of n solid remain CS8Cntially COl1stant so long as the physical conditions,
such !j.S pressure and temperature, do not undergo ally ap preciable change. Liquids
fall in betwccn gases and solids. However, t he t heory of liquids is stil! incomplete
and wil! not be considered in this text.
In mOllt solids the atoms (or molecules) do not exist Ill! isolated entitics; rather
their properties are modified by the nearby atoms. The regular arrangemen t of
the atoms or groups of atoms is one of the most important features of soli d ~; that
is, the structure of solids exhibits 1I. regularity or periodicity constituti ng what is
called a crY$tallo1l.ice; therefore, to understand the structure of a solid, it is neces-
sary to study only the blll!ic unit or cell of the lattice, since all properties rcpeat
from cell to cdl. One of the mOllt effective methods of analYlling a crystal struc-
ture is by means of x-ray or neut ron d iffraction.
From the C/uantum-mechll.nical point of view, determining the structure of a.
solid docs not difftrLfpndamentally from lietcrmining that of a molecule. I ~ con-
sists in finding ~tahle oonfiguration of nuclei" iUtd electrons which are subject to
their electronic interactions and ..... hicn move according to the laws of quantum
mechanics. The two main differences between the structure of a solid and that of
a molecule are the large number of atoms involved Ilnd the regularity in their
arrangelllent. Several typcs of approximations are used to study the structure of
a solid, depending on the dominant factors involved in eRch solid. In this chapter
we shall analyze some of these methods and apply them in order to explain certain
properties of solids, leaving some considerations of a statistical natu re for Chap-
ter 13.
6.2 TlIP@tf 01 Solid.
Solids may be classified aceording to the predominant type of binding. I n this
seetion we shall briefly discuss the most reprcscntative types of solids.
( I) {;ovale,,'. SQlids. In a covalent solid the atoms arc bound together by IOC81-
illed directional bonds similnr to those found in our discussion of the H 2 molecule.
The crystal lattice is determined by the orientation and nature of the directional
bonds. A typical case is diamond, in which the four bonding electrons of each
carbon atom arc oriented n.s sholVn previously in Fig. 5-18 by means of !!p3 hybrid
 (6.2 Typtr oj rolich 'JJ
,
'J2 Solidi 6.2)

-------i. . . . -.. . . .
Fig. 6-1. Diamond lattice.
/,"
---"'

(.j (b)

Fig. 6-2. (a) NIlCllatlice; (b) CsCl lattice.

wave functions, r~ulling in I.he crystal structure indicated in Fig. 6- \. Each ball
represent..'! It carbon nucleus and each bar It pair of locali:l;cd bonding electrons.
The separation between two carbon atoms is 1.54 X 10- 10 m.
Covalent l\Olids, because of thei r rigid electronic structure, exhibit several com
mon macroscopic features. They arc extremely hard and difficull. to deform. All
arc poor conductors of heat and c1cctricity because there arc no frcc electrons to
carry energy or charge from one place to another. Also a relatively high energy is
required to excite whoic-erystal vibrations in a covalent solid due to the rigidity
of the bonds. Wholc-erystal vibrations therefore have a high frequency. Similarly,
electronic c:.:cito.tion energies of covalent solids arc of the nrder of a few electron
volts (ror example, the first electronic c.'(citation energy of diamond is about 6 eV).
This electronic excitation energy is relatively large compared with the average
1 thermal energy (of the order of kT), which at room temperature (298 OK) is about.
2.4 X IO- l eV; hence covalent soilis are normally in their electronic ground state.
i\'lnny covalent solids are transparent, especially diamond, because their first
electronic state is higher than the photon energies in the visible spectrum, which
lie between 1.8 and 3.1 eV.
These solids because they have 110 froo clectrons, nrc also poor cond uctors of heat
and electricity'. H owever, at high temperatures the ions may gain some mob~lity,
resulting in better electrical conductivity. Ionic crystals arc usually hard, brIttle,
and have ll. high melting point due to the relll.tively strong elootrost.atie f?rc~ b~
tWOOII the ions. Some ionic crystals strongly absorb elootromagnetlc radw.tlon In
the far infrared region of the spectrum. T his property is associated with the ene~
needed for exciting lattice vibratio ns. This energy is generally lower for ionic than
for covalent crystals, due to their relatively weaker binding force. Figure .0-3
7
shows the transrllission of infrared radiation through a thin ( 1.7 X 10- m) sodIUm I
chloride film maximum absorption occurs at a wavelength of 6.11 X 10- 5 m or a
frequency of 4.91 X 1012 Hz, corresponding to photons with an energy of
2.03 x 10- 2 eV.
'00
V
80

'" ! \
/

(2) IQnic crys "IIs. At the other extreme arc ionic crystals, which consist of a 0
regular aTray of positive and negative ions resUlting from the transfer of one clec
, trOll (or more) from one kind of Iltom to Ilnother. This is, for example, the eWle Fig. 6-3. Transmission of infrared 0
for NIICI and CsCl, whose crystal structures lire shown in Fig. 6-2. T he sel>arlltiorl radiation through a NaCI film.
hetwccn the Na and Cl atoms is about. 2.81 X 10- 10 m, while the shortest distance [Adapted from R. Hames, Z. Phyrik
betwccn identical atoms is 3,07 X 10- 10 m. The ions arc so arranged that u. stable 75,723 (1932)1 0 - ,o
configuration is produced under their mutual electronic interactions.
50
"
>., IO- a In
00
"

s
. ,
'34 Solid.
,>
/, II 11 111 111 1
Fig. 6-1. Electronic configura-
tions of Li + and F-. Kl!
Most. ionic crystals are diamagnetic because the ions, having II complete shell
structure with all ele<:trons paired, have no net magnet.ic moment.. For example,
ill LiF, the ions Li+ and F- have the configurations shown in Fig. G-4, which
resemble, respectively, the configurations of the inert. gases He and Ne (remember
Fig. 4- 7). This similarity is also refle<:ted in another important property. The
iOlls are spherically symmetric, and thus their binding does not show dire<:tional
preference, as do those of covalent solids. Therefore the ions arc arranged in the
crystal n.s if they were closely packed spheres. T here are an infinite number of
ways of packing spheres. Two common olles are shown in Fig. 6-5: the cubic-
close-packed (ccp) and the hexagonal-close-packed (hcp).
,.,
(.,
,b,
Fig. 6-5. (a) Cubic close-packing (cep) of spheres;
(b) e:<:ploded view of ccp; (c) he.~agonal dose-packing
(hcp) of spheres; Cd) explodf'd vicw of hcp. ,d,
(6.2 6.2) Ty~s of wlich '35
(3) lIy droge rt-lxmd soliW!. Closely related to ionic crystals are the hydrogen-
bond solids, which are characterized by strongly polar mole<:ules having one or
more hydrogen atoms, such as water, H 20, and hydrofluoric acid, HF. The posi-
tive hydrogen ions, since they are relatively small, may attract the negative end
of other molecules, forming chains such lIS
This is particularly interesting in the case of ice, in which the water mole<:ules have
the letrahedral arrangement shown in Fig. 6-6. The relntively open structure of
ice necounts for the larger volume which i~ has by comparison with water in the
liquid phase.
(4) Molecular solids . These solids are made of substances whose mole<:ulcs are
not polar. All electrons. in these moleculC!! arc I)aircd, so that no covalent bonds
between atoms of two ditTerent molecules may be formed. Molecules in this type
of solid retain their individuality. T hey arc bound by the same intermolecular
forces that exist between molecules in a gn.s or tl. liquid: van der IV nal8 jOrce8, which
arc very weak, and which correspond roughly to lhe forces between two electric
di poles. This may be explained as follows: Allhough, on t.he avcrage, these mole
cules do not have a permancnt electric dipole mOlilent, their ele<:tronic configura-
tion at each instant may give rise to an instnntnneous ele<:tric dipole. T he van der
Waals forces result from the interaction of the$C instantaneous electric dipoles.
For the nbove reasons mole<:ular solids arc not conductors of heat and electricity,
have a very low melting point, and are very compressible and deformable. Exam-
ples of molecular solids are CH 4 , C1 2 , 12 , CO 2, CeH8, etc., in their solid state.
Inert gases, whose outer shells are
complete, solidify 88 mole<:ular sol-
ids. Figure &-7 shows the potential
energy curves describing the inler-
netion between t.wo atoms of an inert
gas in the solid state .
Fig. 6-6. Arrangement of water
molecules in ice. [From L. Pauling,
Tilt Not~re 0/ the Clltmicol BOfld.
Ithaca, N.Y.: Cornell University Press,
1960 ; by pennission of the publisher.'
d
 I

,
236 Solidi (6.2 6.2) Ty~, of IOliiU 237

r,IO- H1 m
2 3 , 6 7 8
0

0.'

0.0
,~
K,
~

~
, ,.,
2.0
(the graphite lattice is shown in Fig. 6-8), which consists of layers of carbon atoms
arranged in the form of a hexagon. T he atoms i l l a in.yer are bonded by localized
covalent O'-bonds which use Sp2 hybrid wave functions and nonlocalizcd lI'-bonds,
2.'
as in benzene (SecUon 5.6). T he lion localized lI'-bonding electrons are free to move
parallel to the layers, which explains the electrical conductivity of graphite parallel
to t he layers but not pcrpendiculo.r to them. Successive layers of atoms act M
Fig . 6-1. Van der Waals interatomic potential ene rgy for inert gases. macromolecul~. Thcse layers arc held togcther by wcak van der Waals forces, just
M molecular crystals arc, which account.s for the flaky, slippery nature of graphite.
1n fact, it is because of t his structure that graphite is used as a lubricant. T he
(5) M etal$. Finally, there arc the metals, which are solids of great practical and length of the Sp2 bonds in graphite is 1.42 X 10- 10 m and the separation between
theoretical importance. Metals arc elements which have relatively small ionization the layers is 3.35 X 10- 10 m.
energies, and whose atoms have only a few weakly bOund electrons in their outer-
most incomplete shells. These outermost weakly bound electrons are easily set 00000 00000
free using the energy released when the crystal is formed. A metal thus has a regu-
lar lattice of spherically symmetrie positive ions that remain when the outer- 00000 00000 000000000
most electrons are set free. Throughout this structure there is an electronic ~gas" 00 00 00000 000000000
formed by the released electrons which are responsible for the bonding. These
electrons move, more or less freely, through the crystal lattice and therefore nrc 00000 00000 000000000
not localized. 001000 00000 000000000
l\'letallic solids exhibit excellent thermal and electrical conductivity, for which
the free electrons are mninly responsible, the reason being that the free electrons
(.) (b)
00000000
easily absorb any energy from electromagnetic radiation or lattice vibrations- no 00000000
mntter how small-and thus increase their kinetic energy and their mobility. For 00000 00000 00000000
this same reason metals are also opaque, since the free electrons can absorb the
photons in the visible region and be excited to one of the many c1osc-Uy (lunntum 00000 000000 00000000
states available to them. The free electrons arc also largely responsible for an- 000000 00000 00000000
other characteristic exhibited by metals: their high reflection coefficient. for elec-
t romagnetic W!l.VCl!, especially in the radio-frequency and infrnred regions. ForcCl! 00000 00000 00000000
holding the metal lattice together are spherically symmetric; therefore these lat- 00000 00000 (.)
tices rCl!cmble the closely packed spheres discussed fof ionic crystals. (.) (d)
The l>receding elMS.ificalion of types of solids should not 00 taken too strictly;
some solids are a mixture of more than one type. An interesting example is graphite Fig. 6-9. Impcrfe<:tions in a crystailattice.

..
238 So/irh (6.2 6.2) TYIHS of wlitU 239

T he structure of each of the types of solid th a~ we have described is determined
by the electronic structure of the component atoms, which indicates the type and
number of electrons available for bonding, as well as the energy required to ildjust
their motion to the oonditiOll5 prcvllliing in the lattice (conditions which arc dif-
ferent from those in the isolated atoms). In general, when a solid is formed, a given
amount of energy is required in order to modify the molion of the electrons; how-
ever, much morc energy than this is released in the process of lattice formation.
Crystal lattices arc not perfect, and the imperfections in t hem may be due to
several causes. Figure 6-9 illustrates some of the most typical impcrfcctions. 1n
(n) we have a vacancy left by 1\ missing atom, while in (b) we have a Itubslitulional
impurity replacing an atom of the lattice. Imperfections due to an interSfitial
alom- either of the same type or of an impurity- are shown in (c) and (d). Finally
(e) shows an edge di81OCali01~, which may be looked upon as if an extra layer of
atoms had been pushed halfway through lhe tO I) of the lattice. Lattice imperfec-
tions have a most important cffect on many electric, clastic, and optical properties
of solids.
f:X ..IMI'LE 6.1. Calculation of the internal potential energy of an ionic crystal.
Sof .. ,iQn : Since, in a tiMlt apprOJdmation, we may consider an ionic crystal as a regular
array of poeitive and negative point charges, we may expect that the internal potential
en(!rgy of an ionic crystal is essentially due t{l the electric interaction between the ions.
Let us consider, as an example, the CI.8e of NaCl, and calculate the electric inwraction of
a Na+ ion \\ith all other ions in the crystal. As we can see from Fig. 6-2, each Na+ has
6 CI- ions WI n(!arest n(!ighbon, all at the same distance. Thus, ainee both Na + and Cl-
have charges which are equal in ablsolute value to II, the attractive electric potential
energy of Nil. + due to t he 6 nearest CI- ions is
Thill process oontinu('ll until aillhe crystal is included. The resultant potential energy is
their surn or
H" _ - -4....'-IQR ' + -'-
' - (6 _ -'-
V2 .~.,'R '
v'3 - 3+ ...) - - ...
(6.1)
where Cl is the vulu(! of the sum inside the pnrenthcses, and ill ca.lled MadelllRg'~ CO Il~talll .
In the case of 11 b.ee-centered-cubic lattice sueh a.s NaCI, lhe ~IRdelung constunt is
Cl _ 1.7476. In general, co depends only on th e geometry of the crystal ; for a body-
centered laHice, such a.s CsCI, its value is 1.7627.
Since a is positive, the l>otentiai energy is negat"e and the interionic foree is attractive
at all distances, with no mi nimum. T herefore the crystal should coalesce into n elosely
packed structure with no sta ble con6guration. However, we know that this is not the
case. The conclusion results from considering the ions as l>oint charges. When two atoms
oome very close together the nuclear rellulsion (pu rtiully sc rcc.ned by the electron shells)
and the repulsion among the filled electron shells enter into effect. Therefore we must
add a short-rnnge repulsive term to the l>otentini energy. We did thill before, in Sec-
lion 5.4, ",hen we were discussing ionic bonds. To obtain thi6 repulsive term we assume,
on an empirical basis, a reasonable eXI)ression for the l>otentiai energy. Sevenll expres-
sions have been ProllOl!Cd, but we shall consider only the simple one suggested by the
German physicist, !\lax Born (1882- ):
where fJ and n are two eonstants to be determined. When we use R~ with n > I, the
repulsion ill a short-ra nge force which ill negligible at lnrge distances in comparison with
the eoulomb ionie attraction. When this potential energy ill added to Eq. (6.1 ), the effec-
ti ve potential encrgy is

E!
,.
- 6(-~)
4TIOR
__~(6),
4TloR
E. _ _ L ("- _.!'..)_
411"10 R R"
(6.2)

where R is the distance between nearest ncighbOMl. The next series of ions are t2 Na+ The graph of this potentinl energy is similar to tha.t illustrated in Fig. 5-14. Calling Ro
ions at a distance v2
R, resulting in a repulshe potential energy the equilibrium separation, we have that, at th is dilltance, dB,.!dR - O. Thus

) _ _ ~ (_1!.)_ nil) -
E,_,,(
,.
.'
\4noV2 R 4r,oR V2 (=dE)
dR R_Ra
.'- (.
-- -4no - -+--
R~ RO+l
0

Next follows a group of 8 CI- ions at a distance ~ R, produting an attractive potential orfJ - aRn- ' / n. Then we may write Eq. (6.2) in the form
energy

E. - _ ~ [R'_!. (R')l _
4rloRo R n R

T he nex~ laye r contains 6 Na+ ions at a distance 2R, producing a repulllive I>otentiai The equilibrium potential energy of the Na+ iOI!, obtained by IICtting R .. Ho, is

Ep-4 - 6 ( -'-'-)
4rt02R
~
- - 4:noR (-3). .,'
4TloRo n
( ')
H. - - - - - I - - .
 F
(6.2 6.2)

canceling common factof.'!, we get

""
We find a similar result if we start with a Cl- ion. To obtain the total internal energy of
the crystal, we must add the above result over all ions in the eryst.al. When we do this,
we must make sure we do not count the interaction between each pair of ions twice.
Thus, given that N is the number of ion pairs in the crystal (which in our case is the
from which we obtain
same as the number of molecules), the internal potential energy of the cryst.al is
2vPI M~in!ka.
Nae (I - '!').
2 w _ (6.6)
u- _ 4TfORo n
(6.3)
This equation gives the allowed frequencies in the lattice. Note that the maximum
vslue of w occurs for k _ r Io. The variation of w as a function of k ill shown in Fig. 6-11.
The experimental value of U for NaCI is - 7.77 X IO s J mole-lor - 185.7 kcal mole-I.
Thill re!:lult is obtained by measuring the heat ot formation of the crystal. SUl>3tituting
this value of U in Eq. (6.3), with N equal to Avogadro's number (6.02 X 1023 mole- I)

and Ro - 2.81 X 10- 10 m, 11'0 obtain n - 9.4. For other cubic crystals the value of n
is of the same order of magnitude. This value of n is oonsislent with other calculations. ,g; -----------
~G~ _ _+1
~~:~:--o------o----.
~~_1 e~ ~".J

Fig. 6-10. Linear lattice of identical atoms.

0"--------.1---.
EXAMPLE 6.%. Di8Cussion of lattice vibrations.
"' ;g. 6-] 1. "'requency of lattice
-
vibration~ Ill! a function of k.
So/ul.;ml' The analysis of lattice vibratiolW ill of a great importance because of its bear-
ing on many Ilhysical properties of crystala. T'or simplicity let I1S consider a linear lat-
lice; that is, a row of identical atoms separated the distance a (Fig. 6-10). T he position The fact that there is a maximum frequency means that there is an upper limit or cutoff
of the nth atom is given by:z:. - na. Let UII call ~. the displacement of the nth atom frequency for the elastic (i.e., acoustical) waves in a solid. However, this limit, of the order
relative to the equilibrium position. As a first a]lproximation we shall assume that during of 10 15 H. for most substances, is well beyond the ultrasonic frequencies so far developed
the vibralion.~ each atom interacUi only with il.!! two neighbors.. The separation between in the laboratory.
the nth and (n + I)th atoms hW! increased by ~.+I - ~., and if fJ is the elastic constant
1----1
of the bond, the fOfce 01\ the nth atom to the ri ght due to the {n +
I)th atom is
~)-O---()-O---()-D-X

1--"'--1
Similarly the (n - I)th atom Ilrod uces on the nth atom fl force to the ldt equal to Fig. ~12. Linear lattice comllosed of two kinds of ~t.loms.

Let us 110"' consider a lattice composed of two kinds of atoms of masses M 1 and ;II 2,
Thug the equation of motion of the nth atom i9 arranged alternately 80 that the distance bet"'een neighboring atoms is a and the lattice
apace period is 2a (Fig. 6-12). A typical lattice of this type is an ionic crystal. A calcula,
d'!
M dl2~ = fJ({.+1 - ~.) - fJ({~ - ~.-I) tion similar to that of the pre\'ioug paragraph shows that the allowed frequencies are
given by
- fJ(~.+1 + ~._I - 2~.). (6.4)
(6. 7)
We shall disregard all end effects, and therefore we t ry a solution of the form

(6.5) Now there arc two values of w for each value of k, as illustrated in F ig. 6-13(a). The
upper values of w constitute the opiU:(I1 br(lw::h and the lower ones the MolUliwl braw::h
The term kna gives the phase of each atom and resembles the phase term h: in a wave of the frequency spectrum of the lattice. Actually the silUation is somewhat more com-
]lropagating through a continuous medium. Substituting Eq. (6.S) in Eq. (6.4) and plex than our analysis iml)lies because both the aooustiuJ and optical branches can
 p

24' Solid, (6.2 6.1) Band lMory of ,olidr "3

" t he optical mode shows atronger emission and absorption of electromsgnctic radiation
(}pticnl branch than the acoustical mode. The optical frequenciel! fall in the infrared region of the
spectrum, and hence ionic cryslalll display a strong response to infrared electromagnetic
, ,, radiation. For infrared radiation (where the frequency is of the order of 10" [II and
the wavelength is of the order of 10-4 m), the value of k is of the order of 104 m- I
,,'(2~/M1)ln ,1'0, On the other hand, the value of a for most ionic solids is of the ordcr of 10- 10 m.
, ,7'0 2 And so ktl is about 10 - 6, which is a very small valuc. Hence the regonance frequency
,('l~/MI)'n
,,W of the erystal for elcetromagnetic radiation may be oblained by making ktl "'" 0 in
Eq. (6.7); that;;,
L.I
:T.I,
'\ COlilltital ,,,1'.1 , ,
wo-2{l ( 1-+-
till
1) .
M2
(6.8)
brnnch
,
,,, This, for ex.ample, i>! the frequency corresponding to maximum absorption in the absorp-
0




lion curve for NaCI sho ...'n in Fig. 6-3.
In a more refined analysis, the normal modes of vibration of a solid must be quantized .
(.) When we disregard the sero-point vibrational energy of the solid, t he vibrational energies
(b)
for each mode are mUltiples of 1I",(k). Excitation or de-excitation of a vibrational mode
Fig . 6-13. Acoustical and optical vibrations of n linenr lattice. corresponds to absorption or emission of the energ, 1I",(k). The similnrity to the absorp-
tion or emission of radiation suggests introduction of the concept of a phonon, which has
an energy E - hw(k), a momentum p - Ilk, and which prOllagates through the lattice
with a velocity equal to the group velocity II, - dE/dp - rW/dk. Man y thermal proper-

~
: : ,
. , ' J
ties of wlids, such as beat capacity and heat conduction, can be described in terms of
])honon intcrnctions with the lattice and the transport of phonons through the lattice.

~,
,, ,' , It is even possible to speak of the scattering of phonons by the atoms 6f the lattice (si milar
to the Compton scattering of photons by electrons). This 8catlcring of ]lhonons can be
used to describe the attenuation of high-frequency sound waves through a solid, and the
(a) Acoustical mode thermal effeclll usociated 'I'ith this attenuation .

6.3 Band Theory 01 SolidJl

When we discuss the arrllngement of electrons in solids we may follow a procedure
very similar to the molecular orbital technique used in Chapter 5 for IUJalyzing
molecular structure. When an electron moves past an ion, the potential energy it
feels is the coul omb potential energy, proportional to I/r, as shown in Fig. 6--15(a).
If instead of one ion we have two ions, as in the H 't and H2 molecules, the poten-
(b) OJ/iieal mode
tial energy is like that indicated in Fig. 6- 15(b). For II. very large lI umber of ions
Fig. 6- 101.. Phase relatioll.'lll.mong atoms in the acoustical and optical model!.

oorrespond to longitudinal or transverse (relative to the direction of propagation) vibra-

lioll5, with two transverse modes oorTeSl)Onding t.o the t\\'o indcp'cndcnt directions of
vibration. Therefore, for each value of k there are m possible values of w(k), aa lhown
in Fig. (l--13 (b). The reason for naming the branchCl! "lI.CouStiClll n and "optical" is that
in the acousticnl mode both elllMe3 of ions oscillate in phse, while in the optical mode
they ha\'c a ph~ difference of .... When we oongidcr the transverse vibrations, the (,)
(.) (b)
displacements of the ions in the aeoustieal and optieal model! of vibration give the
patterns shown in Fig. 6-14. As we may see from the figure, the induced dipole Fi,. 6- 15. Coulomb potential energy due to (a) a single ion, (b) two ions, (e) several
momcnt in the optieal mode is much larger than in the acoustical mode, snd therefore ions in II. row.
 po

Solidr (6.3 6.3) Band ihttK":r of rolirb

--~-----r--------------------~
l\-h~-++\---JL\--+\-----p' B,

Fig. 6-17. Energy levels in a linear crystal

III lattice as a funct ion of the interionie
distance.
Fig. 6-16. Types of energy levels in II. linear crystal lattice.

regularly placed in a row, rc&)mbling a one-<iimensional crystal lattice, the potcn-

tial cnergy appears fI.'l in Fig. 6-15(c). If we neglect t he end effects, the potential
energy exhibits t.he same periodicity (or rcgulari~y) as the crystal lattice. An
actual crystal is a t hroo-dimcnsiorml lattice and the potential energy of an elec-
tron moving th rough t.ha lat.tice also has a throo-dimellsional periodicity, repeating
from one cell to the next.
To determine the possible stationary stales of motion in such a periodic poten-
tial energy, we have to return again to the Schrodinger equation. T he solution
will depend on the spc<:ific form of the periodic potential energy. However, the
fact that the potential energy is periodic allows us to obtain a certain runount of
useful information without actually solving SchrOdinger's equation. Let us con-
sider a linear crystal lattice composed of N ions separated the distance (1 (Fig. 6-16).
An electron having an energy such as El cannot move freely th rough the lattice
but is confined mainly to one of the classically allowed regions AB, CD, etc. It
is true that it can go from A B to CD by leaking through the potential barrier
interposed between the two allowed regions (as Cll:plaincd in connection with the
inversion of NH 3, ill Section 2.8), but the barrier is relatively 80 high and wide that.
its penetration by the elcctron is highly improbable. This is why the innermost
electrons in a crystal are essentially localized and their energies and wave func-
InleriQnic disUlnce
Therefore, in a latticc such as that of Fig. 6--16, ench atomic cnergy level gives rise
to N closely spaced levels. Their spacing and position depend on t he interionic
separation, as shown qualitatively in F ig. 6-17. For example, for an interionic
distance a, the possible energy levels fall betwccn P Ilnd Q. When N is very large
the different energy levels arc so closely spaced t hat one may say they form a
continuous band of energy.
Since, according to Pauli's exclusion principle, each level can Ilccommodate two
electrons, one with IiIpin up and the other with spin down, an energy band cor-
responding to a givcn atomic state can accommodate a maximum of 2N electrons
or two electrons per iOIl. The bands arc designated as 8-, p-, d-, etc., according t~
the value of the angular momentum of the atomic state to which they are related.
There are many energ)' bands in a given crystal latt.ice, each corresponding to
one of the energy levels of the atoms that make up the lattice. Figure 6--18 shows
the energy ba.nds corresponding to se~ral energy levels at all interionic distance Q.
I

I
tions, practically speak ing, may be considered the same as in the isolated atoms.
An ~I ectron with energy E2 is not bound 80 st rongly to a particular ion and, by
--- -- -- ..,,---
I

leakrng through the potential barrier, it can move about in the lat.tice. Finally an
eiedron with cnergy E3 is not. bound to any atom in particular ; it has great free- -- j --- I
,
do m of movemen ~ throughout the lattice. These quasi-free electrons aTe not only --1---
,
responsible for most of the collective properties of t he lattice (such as the electric
and thermal conductivities), but. they also provide for the binding of the atomic
---t--
.J ___
iOlls which form the crystal structure.
Our next task is to determine the possible energy levels. We recall the situat.ion I
found in Ht and 1-1 2 molcculCli. The potential energy ill diatomic molecules is I

due to t.wo iOlls and , as a rCliult., the atomic energy levels split into two as t he inter- ~ ,
I
I
ionic distance decreases (Fig. 5-4). Similarly, in linear conjugate molecules having
"IT-bonding electrons-such as the polyenes (Section 5.6)-the electrons move in
a periodic potential energy and each atomic energy level splits into a number of
~1:
0
.'
Fig. 6-1 8. Energy ballds.
Inu.rionie
distance

levels equal to the number of atoms. This was illustrated in F ig. 5-26 for butadiene.
 po

246 Solid& (6.4 6.4) Fru~lec/rOIl model of (I solid

From the energy curves at the right, we can sec that the higher t.hc atomic energy E
lovel, the larger the intcrionic distance at which the bands begin to be formed.
The reason for this is that the greater the cnerlQ' of the electrons, the larger the
region over which they move, and therefore th<l more easily they are afTecled by
nearby ions. Another feature is that. as t.hc interionic distance decreases the bands
begin to overlap. For example, for the interionic distance a', the third and fourth
bands in F ig. 6-18 overlap. This, as we shall see later, is of great. importllnce in Fig. 6-19. Energy of a. free electron RS 9.
explaining t.he properties of many solids. function of k.
Bands associated with the inner COffil)!ete shells in the piI.Tcnt atoms have their
full quota of electrons allowed by Pauli's principle. Electrons in these bands are
also more or less localized, as explained in connection with Fig. G- IG. Therefore o
we shall ignore these bands in our subsequent discussion. However, the band cor-
2.
,

" , .-
2. k

responding to the UPlXlrmost atomic shell, occupied by t.he valence electrons, is

the most interesting ill connection with the solid properties; it is this bUild that we The encrgy of the electroll described by wave function (6.9) or (6. 10), if we
shall consider in more dct!li!. If this uppcrmost band is not. completely filled, it is disregard the constant average potential energy, is
called the canduclian band. But. if it is full, it is called the valence band, and the
empty band just above it. is then called the candzwlia'l band. (l.ll)

corresponding to the kinetic energy of an electron with moment.um p = hI". The

6 . 1 Fnm-Elf!ciron 'Uof/el 01 II SfJlid
As a first approximation in our analysis of the motion of eledrons in the conduc-
tion band, let us ignore the periodic fluctuation of the potential energy and R.%ume
that the electrons move in a region of constant average potential energy. Helice
we may consider these electrons as if they were free and moving independently.
Also, for simplicity, we shall consider a linear lattice. If we assume that the lat-
tice is sufficiently large, our discussion will not be influenced by the boundary
conditions at the lattice ends. Hence the approximate wave function of an electron
of momcntum p = hk is
(6.9)
We consider that k can be either positive or negative to allow for motion in both
the positive and negative X-direetions. For a threc-d.imensionallattice, we must
have a wave function which can be described as follows:
(6.10)
For both wave functions, I ~f = I, which means tha.t the electron has the same
probability of being found at any place in the lattice. This, of course, is not in
agreement with our picture of the lattice as a periodic structure whose periodicity
should be reneeted in the elcctron's prob,tbilit.y distribution . (For example, it.
seems reasonable that there would be a greater probabilit.y of finding an electron
ncar a. positive ion of the bttice than in other regions of the lattice.) However, the
free-electron model, although crude, does provide some insight into the prol>erties
of many solids.
energy as a function of k is illustrated in Fig. 6- 19. The frce-electron model allows
all values of k and therefore of E t , which means that the model does not provide
information about. the width of a band, but. we may estimate it in the following way:
Consider a linear lattice of length L composed of N ions separated the distance a,
so that L = Na. To sustain standing waves, the electron's wavelength X must
saUsfy the requirement n(X/ 2) = I... For each value of n, ~L given stationary state
results. But we know that a band in a lattice composed of N ions has only N
statcs. Therefore the possible values of n are I, 2, 3, ... ,N. Noting thatk = 2rr/ "A,
we then have that
k ~ nrr/ L = nrr/ Na, n= 1,2,3, .. . ,N. (6.12)
T he difference between sueee&,;ive values of k is 11"/ N a, which is very small if N is
very large and justifies treating k as a continuous variable in spite of the quan-
tization condition (6.12). Setting n = N in Eq. (6.12) , we find that the maximum
value of k is
k mu = rr/ a. (6.13)
Thus the range of k-values allowed within the band is between - 1I"/ a and 1I"/ a,
as indicated in Fig. 6-19. T he maximum energy in the band , which is also the
width of the band, is then
h?1I"2
Emu = ;_m,a
;-2' (6.14)
Note from Eq. (6. 14) that the width of the band is independent of the number of
ions composing t.he lattice, a result to bc expected, sillce adding more ions means
 po

248 (6.4 6.4) Pru-e~c/rOfl modtl of a lolid 249

d. TABLE 6-1 Ferm i Energy

"" 1\letal Li Nil. K Rb Cs eu Ag A, Mg AI

E_ ~"C'C'_V--,-_4_.7C2--'-C3_._
12--,_2C'CI4--1-,-1.C8C2..L 1.53 4.07 5.51 5.54 7.3 11.9

o
______- L__
'...
-.~

E_
____ E 1 {a} Ground ltate

(b) ElIcited ltate
per unit volume no is less than the total lIumber of energy levels available in the
band, the electrons will then occupy all energy states up to a ma.ximum energy,
designated by E}', and cll.llcd lhe Fermi energy. If we sct E = EF in Eq. (6.16), we
must have n = no. Therefore for the Fermi energy we obtain the value

Fig. 6-ro. Density of energy states of

froo electrons in a solid.
Fig. 6-2], Distribution of free eledrons
II.mong energy states in the conduction band.
Ef = .!!....
8m.
(3.,):13.
1r
(0.17)

mOTC states; but the periodicity of the latlice, which determines J.:mu according to
Eq, (6. 13), remains the snme (sec Example 6.6),
it is most important to determine how the electrons may dist ribute themselves
in a band among the energies from zero up to Em ..... In Example 2.4 we showed
that the number of energy levels in the energy range dE available to a free particle
enclosed in a box of volume V is given by
dN(~) = 41!"V(!~3)1/2 EII2 dB.
Each level CRn accommodate two electrons (one with spin up and olle with spill
down), Therefore, if we refer to one unit of volume, the total nu mber of electrons
+
per unit volume with energy between Band E dB in the band is
dn = 81f(2;;P Il2 EII2 dB = geE) dE. (6.15 )
Thus the energy distribution of electrons in the metal ground state corresponds to
the shaded area ill Fig. 6-20. When the Fermi encrgy is equal to the energy band
width, the band is fully occupied. Table 6-1 gives the calculated values of the
Fermi energies of a number of metnls.
When a band is not completely full, a small amount of energy is enough to
excite the uppermost. electrons to nearby ellergy levels, as indicated in Fig. 6-21 (b).
However, only the uppermost electrons can be thermally excited, since kT at. room
temperature is about 0.025 eV, which is very s.mall comllared with EF, and the
exclus.ion principle makes it impossible for the low-ellergy electrons to be excited
into nearby occupied states. The distribution of electrons among the energy levels
in a thermally excited state of the lattice corresponds to the shaded area in Fig. 6-22.
The electrons which have been thermally e:>;cited are those with an energy greater
than EF. The states occupied by the e:>;cited electrons fall ill an energy region of the
order of 20 kT above EF.

The quantity geE) = dn/ dE is shown in Fig. 6-20, which is basically identical to
Fig. 2- 12. For a given band the curve should stop at E...... The number of elee
trons per unit volume that can be accommodated up to an energy E is giycn by

Fig. 6-22. Occupation of cnergy st-ates at a

temperature different from absolute zero.
Therdore, using Eq . (6.15), we get

81f(2m!) 1/ 2 {E E' " d}' T he work fllnction of a metal is the energy which is needed to extract all electron
Jo' ~
(0. IG)
n= h3 = from the highest occu jlied Icvel. At absolute zero ~he Fermi energy is the upper
most occupied level. Since thermal energies are very small C(lmpared with the
If the metal is in its ground slate (which, as will be seen laler, occurs at absolute Fermi energy, only a very few electrons are excited above the Fermi energy even
zero), all electrons occupy the lowest possible energy levels comllalible with the at room temperatures. For that reason the work lunction is practically constant
c:>;clusion principle, f\.S indicated in Fig. 6-21 (a) . rr the total number of electrons OVer a wide range of temperatures.
 p

6.5) EIlron molion i,l a ~riodic IIruclurc 25 1

'51) Solids (6.4
In this calculation we ha\'e used the relation geE I'B<B) - g{ b1 Po<B (dg/ dt.1, de-
EXAMP l.E 6.3. DiseUS8ioll of Pauli', apin paramagnetism. rived from Taylor's el<llansion. Recalling Eqs. (6. 15) and (6.17), we have g( ..) .. 311o/ 2lr,
SoI" ,,;,,'I ' The simple free-electron theory we have just discussed is enough to explain and therefore the' magnetization due to the Silin reorientation is
many prol>erties of metals, one of which is the small paramagnetism exhibited by most ,
mt _ 311OJ.!u ~
metals. This paramagnetism was attributed by Pauli to II. change in the states oceupied
by the electrons with spin up and down when II. magnetic field is applied, because the 2l V '
magnetic field favors orientation of the electrons with their "pins opposite to the field.
which is in the same directiou a.~ m and hence is a I)aramagnctic effect. The spin para-
magnetic su~ceptibmty of a metal is thus
,
X .. 311OJ.!aJ'o .
.. 2l V

Fig. 6-23. Oeeupation of energy states
in the presence of an external mllgnctic
field.
We have seen (Section 3.6) that an electron carries a spin magnetic moment pa and
+ (-)
that, in the presence of II. magnetic field Gi it acquires an energy %J.lIl&, where the
aign corresponds to spin up (down) or parallel (antiparallel) w the magnetic field. Given
that E is the total energy of the electron, the kinetic energy of the electron is E =F pB<B,
depending on whether the spin is up or down. Therefore the occupation number of states
with Silin up and down is
where the factor t enteT1! becau.8C in each eMe we consider only electrons with lhe spin
in a given orientation. Figure 6-23 shows the graphs of (dn/dbif and (dn/dE) J (here
we assume that the temperature i.~ close to lI.iJsolute zero). We aee that the number of
electrons with spin down is greater than the number with spin up. Note that we have
maintained the maximum energy equal to fV. Even in the strongest magnetic fields used
in the laboratory (of the order of 0.1 T ), the energy }JB<B is about 6 X 10- 0 eV, which is
very small compared with the Fermi energy, given in Table 6-1. ThUD the two curves
are only l!Jightly separated. Electrons with spin up contribute a magnetic moment -}JB
along the magnetic field, and those with spin down a magnetic moment + }JD. Thus the
net magnetic moment per unit volume of the metal is
OTt - f[,,(:;), -,,(:;),jdE
.. 11'D 1"" [g(E + PB~) - geE - I'B<B)] dE
Introducing numerical values with *,,.,,, 2 eV, we get Xm ,.", (j X 10-'. This value is in
agreement with the experimental result in!lOfar WI order of magnitude i~ concerned. Al-
though we made our calculation M8umi ng a temperature close to abeolute lero, the
result i~ valid for a fairly large rsnge of temperstures.
Note from the above el<prCllSions that since in general no is larger and til is smaller for
d-electrons than for s- or p-electrons, the electron paramagnetism of atoms having in-
complete d-shells is larger.
6.5 Elec tron ,"atlon In tr. "f'rlodlc Structure
To iml>rove the free-electron mooel of a solid, we shall incorporate the effect of the
periodic s tructure of the lattice. Let us start by first looking at the possible wave
functions. I t is clear that the effect of the lattice is to change the free-particle wave
functioll e ... so that, instead of having a constant amplitude, this wave function
hM a varying amplitude which changes with the period of the laWce. Therefore
we write t he wave function fI.!:!
(6. ' 8)
whero u{r ) is a modulating ll.mplitude, repeating itself from one lattice cell to the
next. In the case of a linear lattice of spacing a, instead of Eq. (6. 13) we must
write
(6. 19)
where u(x) satisfies the condition
u(x + a) = u(;r:). (6.20)
Exprcssions (6.19) and (6.20) taken together constitute R/och'a lJuorem. (See
Example 6.5 fo r a full proof.)
Wc may obtain a picture of the wave functions (6. 19) by considering that u(x)
f<.'Sembles the wave function of the isolated atoms and replacing e 1b by the wave

1"'"
fu nctions of a frcc particle in n potential box. Some of the wave functions for the
, ,
.. }JD<B 0 dE dE .. }Jo<Bg{fr). case of n lattice composed of eight iOlls in a row are shown in Fig. 6-24. The band
 pi

252 Solid, (6.5 ,.5) Elec/rOfl motion ill a [nriodic ,/ruc/ure 253
, I ,

,iI /
8

~
\ i : '
,, ,,
V,,,
I ,

,, ,
,I ,
'I\ ,, ,Ii
/."
-L'---r-----i--'>."
"" . /,If'---'I\,,
r----i-:?""---i---+~"':t----j_;r-- Fourt h level
"t"
! /;
Vi
, I V
'N \,'
, ,
I ---" I
I
,
... - - -.... 1
,
II
, I
, ,,
-~---i=i-~--~'~~~~'~
: l-, ... of :
-<
II II II 1 ___ .... ' ....
I Se.:ond level ------,~O,-----'~;_=>>-!r:c~-----,,~,------. , I !I

L J..,...c'
I I .... __
I I I I I ---- I ~',--":c'-.,--,--'--'
I
'
I, I _ _ I ___ , ___ I
__ - II II ~il"St BriUouin IOlIf:

~
I -- I I I I -- I

---~~ -=---_+,-----'~---+'----~'----~,----_+,------_+~.,r-
Sewn d Brillouin lOne
, 1..o""e5~ lewl
I I t J I J I I Fig. 6-25. Brillouin tones in a lincar lattice.
I I I I I I I I
I I I I I I I I
I I
I
I
I
I
I
I
I
I
I
I 'I motion of an electron only when k is close to mr/ a, and the etTect. is to produce

A A A A: : t I
~ ~I I
A I
~ function
Ekclron"'ave
I for ion
each
cnergy gaps. At intermediate values of k, the electrons move freely through the
lattice. The allowed energy bands are those corresponding to the solid lines; these
energy bands are also shown at the right in the figure.
I I I I I I I I
I I I I I I I I It is not surprising that all electron can move freely t hrough the lattice without
I I t I I I I I
encountering any resistance except when k is close to the values n7r/a and the
"i " i'~
"' ig. 6-2-1. Wave (unctions in Il lattice composed of eight ions. perturbation of the lattice is strong. The motion of the electrons in the lattice
can be considered a.s similar to the propagation of an electromagnetic wave in a
crystal. The scatteri ng of the electromagnetic wavc by the atoms ill the lattice
is composed of eight levels, but only four wave functions are indicated. Note gives rise to a reinforced scattered wave when Bragg's condition is satisfied; tha~ is,
that, although the momentum or the electron described by Eq, (6.19) is not. con-
stant, we may still say that fr.k is a sort of average momentum of the electron 2a sin (J """ n).,
(see Examplc6.4). However, the wavelength nssociatcd with 1P(~) is still}., = 2rr/ k,
and thus k is the wave number of the electroJl. where a is the spacing between the plancs Illid (J is the angle tllat the direction of
The energy of the electron is not entirely kinetic, as it is in the case of the free propagation makes with the lattice planes (Fig. 6-26). For normal incidence
electron given by Eq. (6.1 1), because of the potential energy due to the lattice ions.
The expression for the energy in terms of k is complicated and depends on the geom
etry of the lattice. The important result is that the energy has a discontinuity or Incident Scatte~
...,.<!II wa'"d
gap at certain values of k which, for a linear lattice of spacing a, are given by

k = nT/ a, n = :i:: l , 2, ... (6.21 )

The graph of E(l) in this case is shown ill Fig. 6-25. Note from tho."graph that for
values of knot Ilear those given by Eq. (6.2 1), the energy closely res1!mbles that of
... ---.
I,
a free particle (indicated by the dashed line). Therefore the lattice affects the Fig. 6-26. Bragg scatterin g. .
I
---- ---- . --- .... -

(8.5 '.5) 1~'lutNHI motion in a ptriodic flructur~ 255

(6 = 1r/ 2), Bragg's condition becomes 2a = nX. This is the condition to be ap-
plied to a linear lattice for wave propagation along the lattice. For e.xample, if
waves I and 2 (Fig. 6-27) are reflected at successive ions A and A', the reflected
rays I' and 2' have a path difference 24 and a phase difference 2J1"(2a)/ X. For
maximum reinforcement of I' and 2', this phase difference must be equal to 21111",
rcsulting in 2a = 7lX. SeLling X = 21r/ k, we obtain k = n1f/ a, in agreement with
Eq. (6.21). Therefore these values of k arc those at which the linear lattice blocks
the motion of the electrons in a given direction by forcing them to move in the
opposite direction. The m nge of k-values between -1r/ a and + 1f/ a constitutes the
first Brillouin .tQlU. For k betWCCII - 21r/ a and -7r/ a and between T/ a nnd2J1"/ a,
we have the seccnd Brilloui'l lone, and so on.
Heflected a M it moves through the lattice under an externul fore(!, we must usc both F..qs.
"IIVes
I!\~idc!\t 2
:::I'~'~~~~~~~
I'
waVed I
Given that F is the external force on the electron, the work done by this force on
the electron during the time dt is F" dt. This results in a change dE in the ellergy
of the electron. Thus we may write Fv dt = dB = (dE/ dk ) dk . Introducing the
expression for II given by Eq. (6.22) , we obtain
F = hdk/ dt. (6.23)
This can be taken as the equation of motion of the electron in the Inttice. Compar-
ing this equation with the e1assical eql:atioll of motion, F -= dp/ dt., we conclude
that hk plays the same role for electron motion through II. lattice under an e.xternal
force as the momentum 11 plays for electron motion in frcc space under the same
force. For that reason hk is sometimes called the lallice momentum of lM electron.
To describe the motion of an electron (when it is represented by a wave paeket)
(6.22) an~l (6.23). Equation (6.23) gives the effect of Ihe external force on the
electron's "'ave number k and Eq. (6.22) giVe!! the velocity of the electron result-

---------- ---- A A'

,"' ig. 6-27. Omu scattering in a linear lattice.

ing from that force plus the electron's interaction with the lattice. Let \IS first con-
sider an electron in the first Brillouin 7.one nnd su J)J>osc, for example, that the elec-
tron initially has k = 0; therefore its velocity is also 7.ero. When the force F is
applied, k increases according to Eq. (6.23), and from rig. 6- 28 we see that" also
increases; that is, the c\ectron aecc\erates. But when k r(!aches a certain value elose
Recnlling that the group velocity is defined by fig = dw/dk (sce Appendix III) to 1(/0, the velocity begins to decreWle (i.e., the electron decelerates even if the
and that E = Aw, ilCcording to Eq. (1.45), we define the velocity of the electron , force remains the same) . This effecl, of course, is due to the interaction of the elec-
when it is reprcscnted by a wave packet centered about the energy E and wave tron with the lattice. When k = 7("/ 0., the velocity becomes zero but the wave
number k n.!I packet represcnting the c1ectron suffers a Bragg reflection in lhe lattice, k becomes
I dE
-r/a, and the propagation is ill the opposite direction. Obviously the velocit.y
v =-_ (6.22) now becomes negative. If the apl>lied rorce remains the same, Eq. (6.23) tells us
h dk
that k continues changing in the same direction, and thercrorc, since it is negative,
Comparing this equation with the slope of the curve in Fig. 6-25, we conclude that decreases in absolute value. Figure 6-28{a) indicates that the velocity first in-
the velocity of the electron varies within the first Brillouin zone, as shown in creases ill a direction opposite to the external force, but. very SOOIl its magnitude
Fig. 6-28(11.), with similar results for the other zones. The velocity is zero bot.h begins to decrease, since the force is opposed to the velocity; i.e., the electron
at the bottom and at. the to p of the band. At intermediate regions in the band, It decelerates, until eventually the velocity again becomes zero when k = O. From
is very close to the frC(H!leclron velocity, Ak/ m. then on the cycle repeats itself. The acccleration of the electron during the whole
eycle is shown in Fig. 6-28(b). Representing the state of the clectron by a dot ill
0
an E-versus-k diagram (Fig. 6-29) , we can illustrate the process by moving the
. . r. .: U /m ,-
I
--1 dot, &..'J indicated by the arrows in the figurc. If the electron starts aL 0, its repre-
sentaUve point moves from 0 to A, then jumps to B and back to O.
I I
I

I
I
a
I , Let us now consider an electron in the second Brillouin 7.0Ile, which covers the
- 0 0
0
"01 I'
I-
rnnges -27r/ a .:::; k .:::; -7r/ a and 7f/ a .:::; k .:::; 27r/ a. H the electron initially has
I',
I I a k-value slightly above 1f"/ a, the applied force inerellses the value of k until
Y I I k = 27f/a. A Bragg reflection suddenly reverses the momentum and k jumps to
/ I I
I I the value - 27f/ a. If the force continues to act on the electron, k continues to
,.) ,b)
increase (actually decreasing in absolute value) until it. reuches the value - 7f/ a,
when another Bragg reflection takcs place and the momentum is again reversed,
Fig. 6-28. Velocity and aclemtion as a function of k in the first Brillouin lone of n k changing to the value 7f/ a. From then 011 tlu: process continues ill a cyclic
IineaT lattice. manner. Hence the electron describes the cycle C --.,. 1) --.,. E _ F _ C (Fig. 6-29).
256 &J.ids (6.5
- 6.5) ElectroTi mQlum in a periodic &/ruciure 257
,, E
, , The variation of the velocity and the acceleration of the electron in the second
, ,,

~
Brillouin zone is shown in Fig. 6-30. Similar logic applies to the other Brillouin
,
v
zones.
,,, An important com,:iusion to be derived from the above kinematical description
is that an external force cannot rCfl10ve an electron from a Brillouin zone; there-
,,, ;/
fore the electron remains ill the same energy band unless ellough energy is gained
in a single process (as by absorbing a photon) to cro~s the energy gap and pass to
E ,
,,, I "0
the next zone. (There is, however, a certain probability that nil electron ullder an
,, applied force will bridge the gap at k = n"ll/ a; this is called the Zener effect.
~ J ,, However, we shall not discuss it here.)
m'
F C ,, It has been found convenient to define
all effectivt. mMS m + of the electron accord-
m
8," ,A , ,
.. ing to the relation m = Fl o.. Here F is
~
, 0 ,
" " the external force applied to the electron
and 0. the actual acceleration due both to
Fig . ~29. Electronic motion in first and second Brillouin zones in a linear lattice. Under
the ac tion of an external foree, the wave number and the energy of the electron vary within
a wne, II.S shown by t he arrows.
P and to the lattice interaction. Thus we
cannot expect that m will be the same u.s ,
,
, ,
the electron mass me, nor should we cx-
pect. it. to be a con.stant. Considering tlla!.
,
0 ,

2,

,

0 ,

.-
/

2,

Ilk
-
m~

,
0. = dv/dt = (dv/dk) dkldt,

and usi ng EC!.s. (6.22) and (6.23), we have

(6.24)
\ / :,, '
,,
,
Fig. 6-3 1. Effective mass as a func-
tion of k .

--
,
, Note that when the electron is free and it.s energy is given by Eq. (6.11), we have
m = m ... Obviously m is a function of the parameters of the lattice and of the
(.J electron's lattice momentum hk. From the graphs of E-versus-k (Fig. &-25), we
see that m+ is positive at the bottom of an energy band and negative at the top.
It becomes very large, actually infinite, at the inflection point of the ellergy curve;
that is, at the maximum of II in Fig. 6-28. The variation of m+ with k ill the first
Brillouin zone is shown schematically in Fig. 6-31. The values of m+ at. the bottom
of the energy band (nt k = 0) are given for certain metals in T able 6-2.

T ABLE ~2 Effec ti ve Mass

_ ~I
.,, "
-~

,,
0
".,,,
,2,
,, . k Metal
m+/ m. 1.40
L; Na
0.98
](

O.!H
Rb

0.87
C.
0.83

(bJ
We shall complete our description of electronic motion in a periodic lattice by
Fig. 6-30. Velocity and acceleration as a function of k in the 5Ilcond Brillou in zone of a considering the density of states geE') = dnl dE'. We have already discussed this
linear lattice. density for the frce-dectron model !Eq. (6.15) and Fig. 6-20). At the bottom of
 &lidr (6.5
- 259
'"
the band the density of states closely resembles the paraooiic curve of the free-
6.5)

Bo<
E/er/rOIl moliOfl ill a periodic !Irucfure

electron model, but instead of increasing steadily, the curve decreases almost
parabolically at the top of the band. This is shown in Fig. 6-32, which must be
considered as only qualitative. T he actual shape of dn/dE depends on the struc-
tu re of the lattice and the position of the band. T his morc or lc8S symmetric shape
of dn/ dE can be easily understood. Suppose that a band is completely filled. If
one electron is removed (perhaps to the conduction band) , it is possible to say
that a hole has been created, since there is now a vacant state in the band . When
an external force (such as 8.11 electric field) is applied, some electron may be moved Because the normalization condition mskes the first integral on thc right cqual to I, we
into the vacant state, thereby filling the hole. But in so doing, this electron leaves may write
a new hole in the band corresponding to the state it previously occupied. We can
say that the hole moves ill a manner cxactly opposite to that of the electrons
P... - Ilk + P.......
under the applied. fo rce, and thus acts as a positively charged particle. T he zero where P....... corresponds to the second term, and may be considered as the average
of energy for the holes is at the top of the band and their energy is measured down- momentum of the electron as a result of its interaction with the ions forming the lat-
ward; that is, Emu - E. Thcrefore dn/dE at the top of the band is very similar tice, since this is the physical meaning we have attributed to u(x). In this way we con-
to Eq. (6. 15), but with E replaced by Emu - B. clude that the average momentum of the electrons is composed of two parts: the lattice,
or quasi.free, particle momentum Ilk and the momentum due to the interaction with the
laWee.
"
dE
EX A/uPI. 6.5. Proof of B/CJeh'8Iheorem, which ~ tates that u(x) ill Eq. (6.19) is a peri-
odic function with the same period as the lattice spacing.

Fig. 6-32. Density of energy states Solraio'" Lct us consider a linefIT lattice of spacing 0, such that E.(x) _ E.(x oj. +
in a band. Then, since the probability distribution of the clcutrons must show the same periodicity
as the potentia.l energy, we may write
mu
,
O~-----------+--E~--E
'F

The student may realize that in our descriptive analysis of electron motion in Equation (6.25) implies that ,,(x + 0) _ C(x), where C is a qua.nt ity satisfying thc
(6.25)

a periodic lattice, we have blcnded the quail tum and classical pictures of the elec- condition ICl 2 _ l. Thus we may write C _ e;h, where k is an ll.rbitrsry parameter.
tron. We have done this in order to obtai n the basic results desired without be- Then we have the following:
coming involved in complex quantum-mechanical calculations which are beyond
the scope of this book .
Multiplying both sides of the C<{uation by ri~' , we obtain
EX AMPLE 6.4. Calculation of the average value of the momentum of an eicutron e-'~''' (x) _ e-;~('+" ,, (:t: + oJ.
described by the wave function", .. C;bU(X).
This sho'l'!! that u(x) _ e-j~,,,, (x) is a periodic function of x, with period o. By writing
Solution: Assuming that the wave function ~(x) is normalized to unity, we have ,,(x) ~ e;hu(x) , we then have Bl!X:h's theorem.

EXA ,\II' L f; 6.6. Calcula.tion of the width of an energy band using the so-called light-
binding oppronmalion.
Applying E q. (2.50), we may write the average momentum of the elcutron as Solutio", .-\ corl\"enicn t approximll.te wave fUllction-called the tight-hinding approx i-
mation-for all electron moving in a linear lattice of spacing (l is

Pu. - j"(-ih!),,dx. .,.

"I' - '" ,....pL -
L.. e ( na,) (6.26)

 ..
260 lUds (6.5 6.6) CondlJ(;/or', inlu/alor" and .tmiamdlJ(;/or. ,,,
where <I> is the alomic wave function of an electron in a stationary state of an isolated
atom and n - I, 2, ... , N identifies each of the atoms in the lattice. ThUll <1>(:.: - na)
is the wave function corresponding to the nth atom and 'it is a linear combination of
atomic wave functions with cODvenient ],base faet.ors. This wave funclion corresponds
to the description given in Fig. 6-24. Before proceeding to calculate the band width, we
must verify that Eq. (6.26) lI&tisfies moeh's theorem. The wave function", may be
written in the form

which, by oompari&m with Eq. (6.9), gin!s

u(z) - L e-j~('-"J<#>(z - na) .

Then
,,(z+ a) - L e;ll.-t o - 1)Ol<1>[z - (n - l)a].

If the number N of atoms which constitute the lattice is very large so that we may dis.
regard t he end effects, the summations appearing in both expressions of U 8rc identical
+
and u(z) - u(z a), as required by Blooh's theorem.
To find the average energy of an cleetron described by the wave function (6.26), we
apply Eq. (2.51); that is,

(6.27)
" " " " " "
where H is the hamiltonian operator of the electron, given by Fig. 6-33. Allowed energies in the tight-binding aPI)Toximalion.

.' d.ti'2
H - - 2m.. + E,.(z),
and E,(z) is the l)Criodic potential energy of the electron in the lattice. A straightforll'ard
calculation, which we omit, givCII
E..... - E - IX - 2/l cos ko (6.28)
where H is Cll8entilllly the cnergy of the atomic state associated with wave functions
4>(z - na) and IX and {J are allpropriate constants. Equation (6.28) shows that the values
+
of E. .... are between b' - IX - 2{J and E ~ IX 2fj, depending on the value of k. In
other words, the width of the band is 4{J. The v9.!ues of b', IX, and {J depcnd on the atomic
state through thc wave functions <P; therefore there are a seriC!! of energy bands, each
correlated with an atomic state. Figure &-33 shows the expression (6.28) plotted for
several bands. The portions corresponding to each of the Brillouin zonCli are indicated
by heal'ier lincs. The free-particle energy is also shown by the dashed pambola. Note
the similarity to .Fig. &-25. Instead of choosing several ranges of k to express the Bril-
louin Jones, we could h/we limited k to the range --r/ a::; k::; -r/ a for aU bands and
used only the central portions of the curves for the different UIllel!.
6.6 Co ..ductor~ Ill tlu lutor ll, U"" sPm icon d llc tor",
An interesting property of solids is their electrical conductivity. Some materials,
traditionally called iJl.3"Uio1orl, nre extremely poor conductors of electricity
(examples arc diamond and quartz and, in general, most covalent and ionic solids).
Other solids are exceedingly good candudor' of electricity; in this group fall the
metals, such as copper and silver. (To get a qunntit:ltivc iden, consider copper,
whose electrical conductivity nt room temperature is 10 20 ti mes greater than that
of quartz.) lntermediate between these two extreme groups is 3. third class of
solids, called ,emicorniuclor8. Although semiconductors are much poorcr electrical
conductors thnn the metals, thcir conductivity incrcfiSCS with the temperature,
while that of metals decreases with the tcmperature. Typical semiconductors
are germanium and silicon.
One of the most imlX'rtant reasons for the initial success of the band theory of
solids was that it offered a simple explnnatioll of this mnrh.'d!y different electrical
be'havior of solids. We shall make our first nnnlysis by means of the free.-clectron
model, which we shall later refine by taking into account lhe periodic structure of
the lattice.

26' Solidi (6.6 6.6) Conduc/Ot'I, ifilUlalOt'l, and umirollduclOt'I 263
Let us collsider a metal having the bnnd structure shown in Fig. 6-34, which
might correspond, for example, to the energy levels of sodium (Z = 11 ). Bands
corresponding to lhe Is, 2s, and 2p atomic levels are completely fi lled b~ause the
respective atomic shells are al,, com plete. But the 38 band , which can accom*
modatc up to two e l~trolls per atom, is only half fi lled, since the 3s level in each
sodium atom hll8 only one electron. Due to thennal excitalion, SOffie electrons
in the 3s band, which have an energy of the order of the Fermi ellergy for thi~
b..'md, pick up energies of the order of kT (about 0.025 eV at room tempera tu re)
and their distribution among the energy states of the band resembles that of
F ig. 6-22. Under the action of an external electric field, these electrons may,
without v iolating the exelusion principlc, pick up additional small amounts of
cnergy and pn.ss to any of the many nearby empty s~atc:s within the band. I n
sharp distinction to disordered thermal excitation, the electrons excited by the
electric field gain momentum in the direction opposite to t.he field ; t his results in
a. collective motion through the crystal, which constitutes a.n electric current. ,>
T herefore we ooneludc that a substance having a band structurc such as t hat of
Fig. 6-34 should be 1\ good conductor of electricity, and for t he saillc reason it
should be a good thermal conductor, wilh the electrons in t he up permost par- Internuclear distance, IO- IO m
tially occupied band being respo nsible for both processes. In other wo rds, the good
conductors of electricity (also called mtt(Jl~) arc those solids in which the upper- Fig . 6-35. Energy band! or sodium.
most occupied band is not completely filled.

E solid statc the band structure is similar to that of Fig. 6-35 for sodium. The 3s
EmVIY
and 31> bands are indicated schematically in Pig. G-36. Normally, with no ove r~
3,> lapping, the 3s band should be filled and the 3p band empty, and magnesium should
- -- Y band
be all inllulator, as explained below. B ilL because of the overlapping, the upper-
3. most. electrons of the 3s band have the lowest energy states of the 31) band avail-
1I&lf. able. T hus some 3s clectrons move to occupy some low 31)-levels until an equilib-
(---1>'
. ' ;g . 6-34.
ductor.
Energy bllnds in !I. oon-
,. """
,,- ---- '".,} rium energy level for both bands is established. Since the total number of energy
levels Available from the 3s and 3p bands is 2N + 6N = S.V and we have only
'E 2N electrons, there are GN accessible empty states. T herefore magnesium should
be a good conductor; this is in agreement with the experimental ract<!. Those sub-

~3:
2, }
stances whose atoms have complete shells but whi<,;h, in the solid statc, are COII~
2,=:======
h-
ductors because of the ovcrlapping of a filled band and an eml>ty band are often
called 8emimetalt.
B
Actually the situation is slightly more complex because of the possible super-
position of the uppermost bands. Figure 6- 35 shows the actual ba.nd structure of 3,
sodium. At the equilibrium distance ro in the metal, about 3.67 X 10- 10 m, the 3,>
2p level remains practically undisturbed, but the bands oorresponding to the 3s
and 3p atomic lcvels overlap. T herefore the CQnduction electrons have many \ ....-,
more states available t han those corresponding to the 3s band alone. In fact, this
overlapping of the outermost bauds is the oonunon situation for most metals or Fig. 6-36. Overlapping of energy
conductors. For example, consider the case of magnesium (Z = 12). The mag- 3.
nesium atom has the configuration 18 2 2S2 2p' 3s2 , and therefore all the atomic
bands in a conductor.
---:;:,.:--''''0
shells are filled. However, the first excited level, 3p, is rather close to 3s. In the de
=======2,>
 (6.6
- HI ConduciOt"I, WuialOt"I. and umironduciOt"' 265
'" E _ _ __ E
ColldUCliQn
,
baod Empty
__ _ _ _ _ _ } (empty ) :~~tct.l",":'~~~ p
Lo...
_ _ _ __ _ -enera 18P I , Fig. 6-39. Energy bands and

}=ce I elcctron distribution in a semi-

conductor.
---Z~O ____ (filled)
d, Filled
valence

"" "",d
C Si Ce
Fig_ 6-37. Energy bands of an insulator. "' ;S. 6-38. Energy band structure for
diamond (C), silicon (8 i), and gennllnium
(Ge).
In the truns-ilion metals group, such 1\.8 iron, the overlapping bands arc 3d, 48,
nnd 4p, and the number of electrons is insufficient to fiJI thcse bands. Similarly,
in the rarc-earth group, Ole overlapping bands involved Rrc 4f, 5<1, 68, and 6p.
Hence these clemcllt..s, when in the solid slate, are conductors.
Let us now consider the CIISe of II. 8Ub8IMCf! in which the uppermost or valence
band is completely filled Slid does not overlap the next band, which is totally
empty (Fig. 6---37). Since all states of the valence banl!' nre occupied, the electron
energy is "frozen, ~ that is, the electrons cannot change their state within the band
without violating the exclusion principle. The only I>ossibility for exciting an elec-
tron is to transfer it to the cmpty conduction band ; but this may require an energy
of a few electron volts. I(ence an applied electric field cannot a(!celerate the elec-
trons in the valence band, and thus (!annot. produce a net electric current. This
substance is therefore an insulator. (Of course, at a sufficiently high temperature
or under very strong electric fields, some electrons may be excited to the conduc-
tion band, and then an clectric currcnt is possible.) :'>108t covalent solids, which
arc composed of atoms having all evell number of valence electrons, are insulators.
Figure 6-38 shows a simplified band scheme of diamond (C). The bands correspond
to the atomic 29 and 2p levels in diamond, which can accommodate up to 8 elec-
trons. However, thl; carbon atom h!\9 only 4 electrons available for these levels
(remember Figs. 4-7 and 4-10). As the atoms get closer, the 2s and 2p bands
begin to overlap. At smaller illter-atomic distances, they SIJlit again into two bands,
each accommodating up to 4 electrons per atom. (This conclusion is arrived at
by a detailed calculation.) Hence the 4 clectrons from each ntom arc normally in
the lower or valence band, while the upper band is empty. At the equilibrium
distullcc in diamond, about 1.5 X 10- 10 m (indicated by C in Fig. 6-38), the gap
scp:lrating the lowest or valence band from the upper empty band is about 5 eV.
This may be considered as a relatively large energy gap; it explains why diamond
is such a good insulator.
The s!une~and scheme also applies to silicon nnd germanium (except that the
bands correspond to different ntomic energy levels and energies); the equilibrium
separation of the atoms in t.heir solid states is also shown in Fig. 6-38. Now, how-
ever, the gap between the valence and conduction bands at. the equilibrium separa-
tion of the atoms is much smaller ( I.l eV in silicon and 0.7 eV ill germanium), and
this makes it much easier to excite the uppermost electrons in the valence band into
the conduction band. The situation is illustrnted in Fig. 6-39. As the tempera-
ture increases, more electrons are able to jump into t.he next band. This h!\9 t.wo
results: The few electrons in t he upper or conduction bnnd ad !\9 they would in a
metal, and the empty stntes, or holes, left in the lower or valence band act in a
similar way, but as if they were positive electrona (also, their effective mass may
be different because they are in a different. energy band). Thus we have electric
conduction from the excited electrons in the conduction band and from the hole!<
in the valence band; the conductivity incre!\9cs rapidly with the temperature be
cause more tJiectrons are excited to the conduction band. For example, in silicon,
the number of excited electrons is increased by a factor of 10 6 when the tempera-
ture is raised from 250 CI{ to 450 0J(. Hence semiconductors are insulators in
which the energy gap betwC(!n the valence band and the conduction band is about
one eV or less, so that it. is relatively easy t.o thermally excite electrons from the
valence to the conduction band. The energy gaps of some insulators and semi-
conductors are given in Table 6-3.
TA.BLE 6-3 Energy Gaps (eV)
Insulators ,y Semiconductors ,y
Diamond 5.33 Silicon 1.14
Zinc oxide 3.2 Germanium 0.67
Silver chloride 3.2 Tellurium 0.33
Cadmium sulfide 2.42 Indium antimonide 0.23
The electrical conduction in semiconductors which we have described is called
irnriruic ccnduclivity. The conductivity of a 8emiconductor can also be enhanced
by the addition of certain impuritics. Suppose that we replace some of the atoms
of the semiconductor by aoom8 of a different 8ubstance (these atOITlB then constitute


,.. Solidi (6.6 6.6) Conduc/or,. in,u/alor" and 'tm iCOllduc/or, Wi?
,
p ,
} Conduction Conduction o

J -J---
____ =__ [ ban.d mpUrlty [C""",

________ } band
00
o
00 0

0
0
0


,.j Q: holCII (poIIiti'e)
: electrolUl (ncgRtive)
~-'--.
-_::.;"="=
9'-C=:...
=ilmpllrity level!!
Valence
L._ _ _ _ _-' } M,d

,.j ,bj

F ig, 6-W. Impurities in a semiconductor : (a) donors, or n-type, (b) acceptors, or p-type.
..
v

0 0
00 o .
00
o 0 0
0 . 0
the impurity), and suppose that these impurity atoms have more electrons than
those of the semiconductor. For example, if to silicon or germanium, which con- ' bj
- +
tribute four electrons per atom to the valence band, we add a few atoms of phos-
phorus or arsenic, each of which contributes five electrons per atom to the valence
---*o---x
band, we have 1m extra elcctron per impurity atom. These additional etectrons
(which cannot be accommodated in the valence band of the original lattice) Dtcupy
some discrete energy lcyd'! just below the conduction band ; the separation may be
a few te nths of an eV [Fig. 6--40(a)l. These excess electrons arc easily released by v
t hc impurity atoms and excited into l he conduction band. The cxeited electrons
,.j
then contrib\ltc to the electricnl conductivity of the semiconductor. Such impurity
atoms a re called dono,,; thc semiconductor is called fm n-type (or negat ivc)
scmiconductor.
-===+t-=--=-x
Conversely, thc impurity may consist of ato ms having fewer electrons than those
of the semiconductor. F or the cases in which si licoll and germanium arc the host
substances, the impurity atoms could be boron or aluminum, each of which con- v
tributes only th ree electrons. I n t his si tuation the impurity introduces vacant

- oo o. o. :~~
. o :. +

~
discrete energy levels, ,,"cry close to the top of t he valence band ( Fig. 6--40(b.
Therefore it is easy to excite some of the more energetic electro!!s in t he valence
band into the impurity levels. T his procCSII produces vacant states, or holes, in 0 .0 0 .
Q

t he valcncc band. As explained previously, these holes t hcn act as positivc elec-
trons. Such impurity atoms are called acceptor8; the semiconductor is called a
p-typc (or positivc) semiconductor.
V 'dj
-==::::-*o--X
T o produce significant changes in the conductivity of a !>Cmiconductor, it is Fig. ~II . The p-n junction.
suffi cient to have about one impurity atom per milliol\ semiconductor atoms.
Semiconductors have a wide industrial application as rectifiers, modulators, detec-
tors, pho tocells, transistors, etc. ?ilference across the junction [as shown on the right in part (b)1 which, when equilibrium
U! tea.ch.ed, o~rooe:' the further Row of holes and eleetrons ac ross the junction. In t he
EXAMPL E 6.7. Discussion of the p-n junction. ~ucceedlllg dLSCWlSlon we shall conccntrate on t he holes; the situation for the cleetrons
U! equal and opposite.
So hllioll' One important ap plication of semiconductors to modern electric circuitry is D.ue to the recombination of holes and electrons, the number of holes in the n-type
Ihe p-n junction. SU]II>OSe tha t we have two samples of the salnc IICIniconductor-say semiconductor t(!llds to decrease, which allows II. small hole current I I to flow contin-
gcrmanium-one of p-type and lhe other of ntype (Fig. 6-<l 1(a). If the two sam]lles uoualy from the p-side to the Il-aide. At the same time due to thermal excitation hole-
arc placed in contact ( Fig. 6-4I(b, there is a diffusion or flow of holes from the left to eloot ron JlalN!
. are prod ucc dIn ten-type
h . ' and t hese cxces.s holes can
scmlconductor flow
the right and of eleetrons from t he right to the left. This double flow ]lroduees a double Very readily across the junction into the p-side with a :urrent 17. At equilibrium both
layer of positive and negative charges on both sides of the junction, scttiag up a potential hole currell ts are identical; that is, II _ 12 (similar logic can be applied to the electrons).
 p

,,, Solidr (6.7 6.7) Qual!tWl1 tMory oj ekclrical tondutli~ity 269

If 1\ potential difference V i8 applied, &.5 in Fig. G-41(c), with the JHlide joined to the E
J)Ositi\'c terminaIll.nd the n-aide to the lu:gative termi nal of the source of V, the height of E
the potential difference across the junction decreases. Thi!lllllows II larger current J I to
the right, without &etWllly changing the thermally generated current 12 to the left. Thus
II net hole current 11 - 12 results acrOllS the junction to the right, and this current in-
creases very rapidly with V, due to the large sup ply of holes from the p-!!ide. On the
other hand, if the potential difference V is reversed, as in Fig. t>-41(d}, the potential dif-
ference across the junction increases. Thill reduces the value of I., again without sub-
stantially affecting 12, !linee the supply of holes from the noflide is temperature limited.
Thus a net current to the left will cxist across the junction which will approach the --\-----C"!:oo>':-----!.__ , --~~--~~O~~---c!e__
const.a.nt value 12 with incrCa.'J ing V. , , ,
Motion to I('ft
,.,
Motion I.Q rig:h~
" lillian to left '\Iot;on to ri&ht
,b,
F ig . . 6-43. Occupation o~ energy levels in the first Brillouin zone: (a) no electric field
8]lpiJed, (b) external electnc field applied from right to left.
Fig. 6-12. Current lIS a function of voltage acl'OllS
a p-n junction. The voltage V is considered positive
when applied in the direction Jl ..... n and negative with no elecLric field applied, and assume that the electrons are in the first nrillouin
when applied in the opposite direction. ~onc (lhe same logic, h~we.ver, applies to any other zone). The electrons are occupy-
m~ the l~west. states wlthm the band, in II. symmetric form, so that no net current
~X[8ts .(Flg: 6--43(a)~. If an electric field is applied, all electrons experience a force
In a d[~eetlOn ? pIJO:'I[te to the field and, according to Eq. (6.23) , thei r k-values in-
crease III til? d~rectton of the foT(,'e. The result is an Wlymmetric distribution of the
electr?ns w[thm. the metal, as shown ill Fig. 6--43(b). This gives rise to a net
--------~~------v electnc c~rren.t In .the metal, since more electrons move ill one direction than in
tho ol>l>os[te dIrectIon.
As long ~ the e1eetr~e fi~d is applied, the occupation of states with k parallel
to the force mereases With time and the occupation of those states with k 0 't
decreases 'th t' 1 th ppos[ e
. ';[ [me. . II 0 .er words, the curren t increases continuously with
Figure 6-42 shows the graph of the !let current acro~ the junction 8.S a function of V, time, even If the electrIC field [s constant, due to the continuolls acceleration of the
with V considered positive when applied as in Fig. 6-4 1(c) and negative otherl\ise. The electrons. (We shaH ignore the oomplex elTects that may result when some cleo-
net current is expressed fairly accurately by the expression
~on8ev~ntuallY reae~ the bou~dary of the Brillouin lOne at k = 7r/ a; this problem
as previous ly been diSCUssed ll\ Section 6.5.) The above result contradicts experi-
el\c~ .. Most conductors obey Ohm's law, which may be written either in the
We conclude that a p-n junction acUs as a rectifier or a dele<:tor device favoring the f9.illlhar form I' = RI or in the morc oonvcnient form
passage of a current in the direction p ..... n. This is the same function performed by
diode and triode electron tubes, but the p-n junction may perform it with an expenditure i = ue, (6.29)
of considerably less energy.
whcre i is the current dens ity, expressed in A m - 2 e is the applied electric fi Id
. m N C-' ,andUIS
expressed' ' th ecoHuucllUilyoflhesubstance
_J . . ' c ,
expressed in 0- 1 m-I
6.7 "IIant"," Th efJrll of Elf..'f':trie nl Con""etir;itll T he rec[procal of the conductivity, '
In the preceding section we have discussed electrical conduction in solids from the p = l/u,
point of view of the free-electron model. The periodic slructure of the solid must (6.30)
be taken into aeoount, however, and the results of Section 6.5 must be used in is called the remtivily, and is expressed in n m.
order to obtain (IUantitative results. For simpliei~y, we shall bWle our discussio[l a I n either of th~ two forms, Ohr:l's law st.ates that a consto.ntelectric field produces
on a (lIlc-dimensional model. Let us consider the solid to be in it.!! ground state, COnstant electnc current; that IS, when all electric fi eld is applied, the conduction
 0:

270 (6.7 6.7) QUalltum Ihlf)rY 01 tftdrirol corlduclieily 27/

electrons in a metal acquire an average and constant drift velocity. Therefore we spread centered about. the wave number I.: . The motion of n wave pllCket may be
conclude that there must be somc mechanism which prevents the electrons under hindcred by scattering. Initially the wave packet is moving in a particular direc.
the applied electric field from acce\cTntin!- indefinitely up to the to p of the con- lion wilh the wave number I.'; nfter the se!~ttering it is moving wi th a d ifferent
duction band. wave number, say k ', in a different direction. III other words, scattering produces
In the classicnl theory, formulated by Drudc and Lorentz before thc advent of a transition I.. --+ k '. I n the transition , some momentum and encrgy arc transferred
quantum theory, this constant avemge velocity of the electron resulted from the ~ the sca.tte r~r. :h~fTect of t he applied ele~tTic. field i.s to nccelerilte the electrons
frequent collisions of the electrons with thc positive ions which constitute the III a certS\II directIOn ; the efTect. of the scatlermg IS to (hsarray the electron motion,
mClallattice. In such collision.'!, an electron was supposed to trallsfer the momen- hindering the accelerating cffect of the electric field.
tum it had gained from Ole electric field since the previous collision to the iOIl, and
this prevented the electron from being accelerated continuously as it drifted in
the direction OPl)Ositc to the applied electric field. This mechanis.m also explained
the Joule effect as being due to the energy gained by the ions from the electronic "
collisions. In the Drude-Lorentz theory, the cond uctivity is given by
," into
&.nerin/t
~I}~Y Itllte!
(6.31) ,"
0

where n is the number of electrons per unit volume and 7" is a pnrameter called the
,, 8
relaxation lime. This c,'l:pression can be derived as follows. T he acccleration of an .~
,
electron due to the applied electric field is a = - ee/ m. If I is the time between :~ ,
two successive collisions of the electron with the lattice ions, the average drift
velocity of the electron is v.,. = iat = -e(e)I/ 2m. T he current densit.y is then "
j = - env."., = (ne 21/ 2m. )&, which yields a = 1!e 2t/ 2m.. Comparison with
E<I . (6.31) shows that T = it Hence in the Drude-Lorentz theory the relaxation
time 7" is assumed to be of the same order of magnitude as the lime between 1.\\'0
o 20 40 00 SO 100 - -'.- ---"''II0'''-- -+-,
Tcmptn.tll,,", - "
successive collisions of the electron with the ions of the lal.tice. For most metals
at room tcmperature, the value of 7", computed from the me!\SuTcd value of a, is Fig. 6-1-1. VariatiOIl or resistivity with Fig. 6-,15. Scattering of clcctrons ill fil'llt
of the order of 10- 14 s. Given that i is the average separation of the ions alld v, temperature. Brillouin zonc by impurities.
is the aver:'lge thermal velocity of the electrons in the absence of the electric field,
we can assume Hmt the relaxation time is of the ordcr of mngnitude of l/ v,. For
most solids l is of the order of IO-~ m. Using for the electrolls the same relation . A steady 8t1l.[e is produced whcll these two effects b1l.lance e1l.ch other, in II sta.
derived for gas molecules, v/ = ..,f3kT/ me (sec Section 10.6), we find that at room \Jstical sense, resulting in a constant average velocity of the conduction electrons.
temperature v/ is of the order of IO~ m S-I. Then I/v, _ 10- 14 s, in agrecment For this situation to exist, the scattering illust occur at flny k-vlllue within the
Witil the experimental value of 7". However, at temperatures tbat are low (but conduction band. Consider, for example, tile onc-dimensional case showll in
1I0t too close to absolute zero), the conductivity of metals varies approximately Fig. 6-15, which is similar to Fig. 6-43(b). Since scattering cannot violate the
as the rceiprocal of the absolute temperature (that is, a ..... I / T or p - T) , as exclusion principle, the electrons must be scattered into vacant stiltCS. T hus the
shown in Fig. 6-44. for sodium. This mcallS that the relaxation time also varies electrons that are . scattered are the most energetic ones. T hese electrons are
reciprocnlly with the tcmperntllre. scattercq into vacant states which, in a linear 19.tticc, have opposite momentum
When we compare the c,'l:perimenlal value of T at low temperatures with that of and (in general) lower cnergy; the figure indicates this scilcmaticnlly. T he cnergy
i/ "" in order to obtain II quantitative agreement we would have to assume values lost by the electron is absorbed by the scatterer. The result is that the most eller.
for I mnny times larger thall the interionic separation. This was one of the first getic electrons frequently reverse their motion, thereby checking the accelerating
elues that the Drude-Lorentz theory WM not correct. effect of the electric field. The number of electrons moving to the right and to I.he
Hence we shall first try, using the (Iuanlum theory, to explain why the dec Icft is maintained at a statistically constant difference, giving rise to a steady cur-
trons maintain !~ CQnstnnt average velocity, and next obtain II qualltital ive expres rent. Although we have used a one-dimensional model, a similar situation exists
sion for the conductivity, simill\T to Eq. (6.3!). for the three-dimCllsional case. We then sec th1l.t t he idea of SC1l.tlering of the elec.
In the quan tum theory, an electron il:l repTCSClltcd by a wave packet. There is tron wave packet aCCQullts for both Ohm's law and the J oule effect. The latter
an cnergy spread centered about the energy E and an ussociated wave-number results since energy and momentum arc transferred to the scatterers.

'" Solidi

Since we have I)fcviously seen (Section 6.5) that an electron can move freely
(6.7 6.7)

It is naturn.l to assume that 1:, is proportional to the number of scattering centers

through a crystal lattice (except when k ,.. 7r! a), our next lMk is to identify per unit volume, designated by 71, (expressed in m- 3), and so we may write
the sources of the assumed scattering. The general answer is the following; any I. = 71011.. whereu. (not to be confused with the conductivity) is called the seal-
irregularity in the periodicity of a [Mtice disturbs the otherwise frcc motion of lerifUJ crOlls MeliQn per center (it is expressed in m 2).
the eledron, and the disturbance call be considered as a scauering. These lattice We can calculate (I . by using the techniques of quantum mechanies if we know
irregulari ties arc due to two factors: ( I) ImperJectiQ1U in the lOI.id. such as vacant the interactil)P between the electron nlld the seatterer. The Fermi velocity Vv is,
spaces, interstitial and displaced atoms, dislocations, and impurities; for example, by definition, tcmperature indel)Cndent. Also, in the case of lattice imperfections,
if small amoun ts of impurity atoms are added, and these arc uniformly distributed the terms appearing in t . are basically temperature indcpendent. Thus we verify
throughout the solid, the conductivity is modified. The contribution to the COII- that the conductivity due to lattice imperfections is independent of the tempern-
ductivity due to scl\ttcring by imperfections in ~h e lattice is essentially independent ture. On the other hand, it is reasonable to lISSume (and it can be shown theo-
of temperature. (2) Thermal 08Cillalory motion oj the ions which cOIlSlitute the retically) thai for lattice vibralionsu. is proportional to the square of the amplitude
lattice. Since the ions do not all oscillate in phase, their vibrations give rise to small of the ion oscillations; that is, (I . _ A 2. But the energy of an oscillator is propor-
flu CLUations in the lattice spacing ; although t hese fluctuations nrc smnll, they are tional to the square of the amplitude, and we may write
spread over all the lattice. In addition, because the oscillations increase the effec~
tive crOSlJ section which the ions present to the motion of the clectrons, the prob- (I . - vibrational energy.
ability of scattering is proportionately larger. Clearly the lattice-vibration effect
is teml>cmture-dependent, since the amplitude of the vib rations depends on the At. temperatures not too close to absolute zero, the average vibrational energy of
vibrational encrgy and this in turn depends on the tempemture. a solid is proporlional to the absolute tcmpcrn.ture T. Therefore we conclude that
(I, _ T, which, according to Eq. (6.25), means that T _ l i T. Therefore, in view
To be more quantitative, we may still use Eq. (6.31) 10 eXI)rcss the conduc~
ti vity, replacing the electron mass me by its effective mass In-; t hat is, of Eq . (G.23), we havc that (I _ l i T. We thus verify that the conductivity due to
lattice vibration has the proper temperature dependence.
(6.32) If t, ,; is the macroscopic cross section due to t he impurities and I . , is that
due to the thermal vibratiolZS of the lattice, we have 2:, = 1:. ; +
2: .... 80 long as
In geneml we can calculate m- at the Fcrmi energy ~v , sinee the energy of the we may assume that the two scattering probabilities are ndditive. Therefore
conduction electrons is not very different from fV. Also 11 is not the total number l i T = vrI. = VV(Z . i + t . ,), and we may write the resistivity of the metal as
of electrons per unit volume in the conduction band; rather it is the effective
number of electrons which participate in the conduction. T his number is smaller 1 m"vv .
than the total number of elcctrollS in the conduction band, due to the restrictions p-
-
- - -71-2011( r '.'+ z ,., )-
(I -
- p..+ p.. (6.35)
imposed by the exclusion principle.
Given thnt p . is the probability of scattering of the electrolls per unit time (thus where Pi is the resistivity of the metal due to the impurities and therefore is esscn~
it is expressed in S-I), t he relaxation ti me is given by tially tcml)Crature independent (but varies from one specimen to another), and
PI is the resistivity due to thermal vibrations; P, increases with the temperature
T = l i P . (6.33) and is the Bame for all specimens of the
snme metal. Equation (0.35) expresses a 5
In other words, the larger the scattering probability, the smaller the rela.xation wellknown experimental result, known
time and the smaller the conductivity, Z\8 our physical model requires. Let us as Mathiuu11.'s rule. The quantit,y Pi is ~ 4
designate the scnttering probability per uni t length by I , (thus it is expressed in called the residual resistivity. Figure &-40 1-
m- I ). This quantity is also called the macroscopic scall~ring crou 8OClion. The shows the resistivity of three specimens of - 3
conduction electrons move with lI. velocity very close to thu.t corresponding to the sodium with different impurities in a ...
Fermi energy E.'. Designating this velocity by vr , we have that P, = vvI., and tcm!>cralure range below 20 oJ{. The .~ 2
F..q. (6.33) beeomes Curves show the validity of Eq. (0.35) . ,
.ijj

O'~~'~ 6;=~8;:~'O;:'~'~':':".6-!'8'-~20'-' '
(6.34) Fig, 6-46. Resistivity of three differe nt
samplCII of sodium. (Adapted from D. Mae-
The problem ha.s thus become one of calculating I .. This is a d ifficult problem Donald and K. Mendelswhn, Proc. ROil. Soc.
which is beyond the scope of this text. However, we can malott cert ni n estimates. (London) A202, 103 ( IMO Teml'"... t\l~, OK

274 (6.8

B'{l
6.8) Radiaiir:oe /roruiliorn ill lOIidt 275
6.B "adlatl,;e Trant,ilion" In Solid"

8{H'{~
AbI!orption At..:lrption
So far we have developed a model of solids, the band theory, whiell accounts for
most properties of solids in a consistent fashion; this, of course, is the most a
physicist may expect from a model. But. is there any direct evidence of the exist.-
ence of crlergy bands slid energy gnl>81 Is it possible to measure the Fermi energy'!
The nllswcr to these questions is yes. Perhaps the moot. direct evidence comes from
radiative transitions in solids. We shull first discuss x-ray emission and then some
II{
.. 0
(.)
I'hoton energy
0

(b)
I'lwton energy

absorp tion I)rocesscs.

-"IT L1= H'{ "'{-

AiJIIOq)tion A1Mo'1)tion

Fig. 6-47. X-ray electronic transition

from lhe uppermost band into a vacant
--i!t
inner atomic state; (a) conductor, (b) in-
sulator. Inner, 8{ I ". 8{ lui
lltom'c"_ _--'_ _ 0
Photon ~nergy
level
(.) (b) (.) (d)

X-ray emission ill atoms results when an electron occupying one of the outer
shells falls illto a vacant state left in one of the inner or low-lying inner shells
(Section 4.7). According to the band theo ry, we may say that x-ray emission in
solids takes place when, for example, nil electron in the uppermost hand undergoes
a transition into a lower-level band where a vacant stale exislS, as indicated in
Fig. 6-47. These vacant statCfl are produced by electron bombardment or by ab-
sorption of radiation. The lowest or fina l energy level in the transition is prac-
tically identical with the atomic energy levels since, as explained before, such
levels arc not affected when the solid is formed.
In the atomic case, a given transition corresponds to initial and final ellergy
levels of well-defined energy, resulting in l\ photon of a certain energy or a sharp
line of a given wavelength. But the band theory suggests a different situation in
the case of solids. The electron making the transition can start from any of the
possible cne.rgy levels in the uppermost band, and therefore the. ene.rgy of the
emitted photons has a spread of the. order of tF (that is, the photons have energies
between Eo and about Ho + ty). In the case of an insulator, the energy spread
is equal to the width of the band. Therefore, instead of a single x-ray line, the
8~tru m consist.s of a band of wavelengths. This in fact is what is observed ex-
N. Mg
o 2 3 o o , ,v
10
Fig. 6-48. Intensity distribution or xray transitions for sodium, magnesium, and
aluminum. (Adapted from II . O'UrYlln and H. Skinner, Ph l/'. Re~. 45. 370 ( 1934).1
Fig. 6-49. X-ray absoq)tion transitions in II. solid .
perimentally. figure 6-48 shows the experimental intensity dis tributions for the
x-rll.y transi tions to the 2p level for sodium, magnesium, and aluminum. These
intensity distributions arc computed thcoretieally by multiplying dn/ dE, the num-
ber of electrons per unit volume a.nd per unit energy range around the energy B,
and the probability T (E) of a transition from energy E in the band into the lower
energy level. That is,
1(1 ~ (dll/ db"') X T (E,').
We have already considered the Quantity dll/d t: in Section 6.4 and we can com-
pute. T( B) according to Quantum-meclmnical methods (see Section 2.11). A sharp
droJl of the intensity obviously occurs for E - fl'. III fact, the energy spread
shown in the. graphs of Fig. 6-48 is of the same order of magnitude as the values of
fp given in Table 6- ), The I>caks sho'vn by magnesium and aluminum are due to
the contribution of the electrons in the 3p band, while in sodium all electrons are
within the as-band .
Let us now consider the ease of absorption. Figure 6--49 indicates some typical
s.ituations. In (a) we have. a conductor with the uppermost band B partially filled
and sepnrated by all energy gnp from the empty band B'. Electrons in B can be
excited into nearby empty states in tile same band when they absorb photolls
with energies from zero up to the energy required to reaeh the top of the band.
The other photons that can be absorbed arc those that take an electron from B
into B'. Therefore the absorption spectrum has the shape shown in J<~ig. 6-49(a),
with a gap for the energy region at which no photons can be absorbed. 1 the
bands Band B' overlap, as in Fig. G-49{b), no energy gap exists and a conlin-
uous absorption spectrum results. In the case of an insulator (Fig. 6-49(c), only
transitions from the valence bnrld B into the conduction band 8' arc possible.

276 (6.8 Referenct, 277

Therefore, to induce transitions, the photons must have a minimum energy of a Condu= ~ -....,
feweV. The resulting absorption spectrum is as shown in Fig.6--49(e), This would
~
:;z.L . . . .
also be the case for semiconductors, except that due to the smallness of I.hcir energy Impuril - -
gap. some electrons occupy band 8' j therefore the abliOrption spectrum resembles "" -
~ """ -<
~
Forbidden
the situation illustrated for ease (b), Lattice defects, mainly impurities, have im- traMition
portant consequences. They introduce new energy levels, which may fall in the Valen"l! Holo
energy gap (Fig. 6-49(d). Electron transitions into these energy levels allow "."
absorption of photons of much lower energies than needed to go from B to 8',
and the absorption spectrum is as shown. _
(., ~, (., (.,
Photons in the visible region of the electromagnetic: spectrum have energies in Fig. 6-50. Me<:hanism of luminescente.
the range 1.6 eV up to 3.2 eV. A 50lid is transparent or opaque depending on its
absorption properties in that energy range. For example, conductors and semi-
conductors are all opaque, since they have absor ption curves similar to that given may fait into an energy level called 9. trap, from which a radiative transition to the
in Fig. G-49(b). Pure insulators are trallsparent if Eo in Fig. 6-49(c) is larger ground-state impurity energy level is forbidden (Fig. 6-5O(d. In such 9. case,
than about 3.2 eV. But if, as a result of the impurities, the peaks E; in Fig. 6-49(d) the electron is in a state similar to an atom or a molecule in a metastable state'
fall in the visible region, the insulator is colored (or even opaque). For this reMOn the tra~pcd electron must wait until, by some mechanism, it is returned to th~
thesc impurities are also called co/or centers or F-cenlers (from the German farben: conductIon band, after which it follows steps (b) and (c), as shown in Fig. 6-5O{e).
color). For example, pure corulldum (AI 20 3 ) should be transparent, but ruby ?ue to the time delay involved, which may amount to many seconds, the process
(which is AI 20 3 with a small chromium impurity) shows a strong red color. This IS called phoaphorucence. These substances are t herefore clllled phOBphors. One
is because the chromium atoms induce a strong absorption in the green region of such substance is zinc sulfide. Phosphorescent materials Ilre used in the screen of
the spectrum, resulting in a red color of the solid whell it is illuminated with cathode-ray and TV tubcs, as well as in scintillation detectors which are used to
white light. detect "Y-rays. A phosphor widely usoo in scintillation detectors is No.1 activated
with Tl.
Anothel important radiative property of solids isluminescenu. In general, when
the electrons in atoms, molecules, or solids are e.xcited by some means (e.g., absorp-
tion of radiation or electronic bombardment), there are several processes which
compete to bring about deexcitation (e.g., radiative transitions a.nd inelastic R elerenee8
collisions). In some installees the favored process is radiative transition and the
substa.nce glows when it is illuminated with radiation of the proper wavelength, l. ""Iaterials,n &i. Am., September 1967, the entire issue
or is excited by some other means. Substances having this property are called 2. "Modern Study of Solids," J. Patterson, .4"1. J. PhV'. 32, 269 ( 1964)
luminescent. Luminescence in solids is closely related to impurities and lattice 3. "Quantum Physits in Ameriea Between the Wars," J. Slater, Phy.KS Today,
defects. Figure 6-50 illustrates some procC.l$SC$ that take place in luminescent January 1968, page 43
solids. When an electron is removed from the valence band into the conduction 4. "The Structure of Crystal Surfaces," L. Germer, Sci. Am., March 1965, page 32
band, a hole is left in the valence band (Fig. 6-5O(a. In a perfectly pure and 5. "Resource Letter SC R-t on Semiconductors," P. H!lIldler, .4"1. J. Phy. 32, 329 (1964)
regular lattice, the elcctron usually returns to the valence band, although it may 6. "Energy Propagation in a Finite Lattioe," W. Band and A. Bhatti, .4"1. J. Ph".
take some time to do so, since both electron and hole have great mobility and they 33, 930 (1965)
may wander in difTerent directions. However, if the lattice has some impurity
7. Inir/XI udio'l to SemicOllductor Phyric., R. Adler and R. Longini. New York: John
which introduces energy levels in the forbidden region, an electron in a low-lying Wiley, 1963
impurity level may fill the hole in the valence band, while the electron in the
8. EfemenJo'll Solid State PhyRc', C. Kittel. New York : John Wiley, 1962
conduction band may fait into one of the (normalty empty) high impurity energy
levels, as shown in Fig. G-5O(b). These transitions generally involve photons of 9. Structure of Matler, W. Finkelnburg. New York : Academic Preu, 1964, Chapter 7
small energy which do not fall in the visible region. Finally, the electron may 10. Quantum Theor" of Matler, J. SlaU:r. Ncw York: ~lcGraw-HiIII951 Chapters 10 12
13 and 14 " , ,
fall from I,he high-energy impurity level to the empty low-energy one, emitting
radiation of less energy (or longer wavelength) than the incident radiation; this II. TM FeYflmafl Lture, on Ph,,8U' , Volume II, R. rcyDman, R. Leighton, find M.
constitutes the luminescence (Fig. 6-5O(c. In some instances, instead of going Saads. Reading, MaSIJ. : Addison-Wesley, 1963, Chapter 30; Volume Ill, Chaptel"ll
t hrough the procC138 shown in Fig. 6-50(b), the electron in the conduction band 13 and 14

Problemlf
6.1 Show ~ha~ the number of carbon-
carbon bonds in diamond ilI lwiee the num
ber of carbon atoms (see Fig. 6-1). The
energy required to dissociate one mole of
diamond is 170 kcal. Dewrminc thc energy
per bond and express it in eV. Compare
th is energy with the energy per bond in Sp3
compounds. _ ation falb in the infrared (wavelength
6.2 The Madelung conslant for the cubic
ZnS structure i~ 1.638. Calculate ~he bind-
ing cnergies for ZnS, for which TO - 2.35 A,
and CuCI, ....' hi ch has the same structure
for which TO - 2.34 A. The experimenla l
valuCll are 37.9 eV I molecule for znS and
9.8 1 eVI moleeule for CuCI.
6.3 Calculate the binding energy of C3Cl,
for which TO - 3.56 A. Compare with ita
experimental value of 6.72 eV I molecule.
6.4 The bulk modu lus of a solid is defined
as IC - -(II V )(aVl ap). When the energy
is only a function of the volume, the above
definition iscquivalent to IC _ V(d 2 UI dV2).
Show that for an ionic crystal,
1&...oR~
Compute the bulk modulus for NaCI, as
3uming that n _ 9. Compare with the
experimental value of 4.2 X lOll N m - 2.
6.5 Sound velocities in solids are of the
order of magnitude of 3 X l03m s- l
Interatomic distanct'll in solids are of the
order of magnitude of 3 X 10- 10 m. Esti-
mate the order of magnitude of the cutoff
frequency, assum ing a linear lattice.
6.6 Show that for small values of kll, the
t wo values of w given by Eq. (6.7) can be
approximated by
, (I
w - 2{J MI+M2
I)
6.7 Show l hat for k _ r/ 2c., the two
values of w given by Eq. (6.7) are
and w2 _ 2fJI Al 2.
6.8 In m031 diatomic ionic crystals, res-
onance absorption of electromagnetic radi-
about IO-t m). The interatomic diManee
is of the order of 2 X 10 - 10 m. Es timaw
the erro, made wh en Eq. (6.8) is used to
oblain the resonance ab!lOrption frequency
of infrared radiation by the crystallaUiee.
Assume that AI I and AI 2 are the m&!!SeS of
sodi um and chlorine atomg, respectively.
6.9 Usi ng t he frequency of maximum
absorption from t he absorption curve of
NaCI given in Fig. 6--3, compute t he clas-
tic con.'llant Il of Eq. (6.8) . Calculate the
cutoff frequencle3 for both the acoustical
and optical branches of oscillation.
6. 10 The interatomic distance in most
melals is of the order of 4 X 10- 10 m.
Estimate the width of the condu ction
band. Compare with values of the I<'ermi
energy gi ven in Table 6-1.
6.11 Calculate the number no of elec-
trons per unit volume in the conduction
band of lithium, copper, nnd aluminum by
using the Fermi energy values listed in
Table 6-1. Compare your resul t.s ..... ith the
num ber of valence electrons pe r unit
volume for these atoms.
6.12 Estimate the width of a band in
metallic sodi um, using Eq. (6.14 ) and an
equilibrium distance between ions of
3.67 X 10- 10 m. Comllare your estimate
with Fig. 6-35.
6.13 Sodium has a density of 9.7 X
1 0~ kg m _3 . Ass uming that each atom con-
trib utes one c!eetron to the condu ction
band, determine the Fermi energy for s0-
dium. Repeat for calcium, assuming two
electron3 per atom are cont ri bnted to t he
conduction band.
Probltr/U 279
6.14 Estima te the Pauli paramagnetic
susceptibility of !!O(lium. COlllpnre with
Ihe e:l:perimentlil \"Illue of the magnetic
~u:>cepti bility of sodi um.
(1.15 It can be shown that the boundaric~
of the Brillouin zonc~ ill a two-dimensio nal
~qUllrC lattice of side 1:1 arc gh"en by tho;>
values of k~ and k., satisfyillg th e t'<tu ation
",here 111 li nd I!~ ure !>OIlitive or no;>galivc
integers. Plot the boull(iIl rie8 of the Bril- F igure 6-::; 1
louin zones, Il,jug k~ and k. llII coordinatcs.
Try to vi~lllll ilC the energy surf:l ee if Ihe
the resull. [llint: Xcglcet lerm~ in volving
energy is pio\t('(i on Ill! axis perpendicullir
to the kz-k. plano;>. ;\ot(' illcid('ntally that tll"O ",functions if they are more thlln one
ecl! ZllJarL)
th e abovc cqulItion rcducc~ to Eq. (6.21 )
for a ]ill('ar httice. [/ii'll; :\lltk(' nll Jlos.;ible !U9 SUPI>OSC thM an clcctffin moves on
combinat iOIlS of III and n2 e~lual to 0 , ::I:: I , a circular ]lath 'ilong which there are
2, . .. and J1lo t thc rc~ulting equations.] .\' ions equnl!y ~I),"eed the di~l:lnCe (I
(Fig. 6-51 ). (a) l bing wal"e functions of
6.16 l "ing " procedure similar to tha l of
Exa mple 6.-1, ~ h ow that the average cncrgy the Bloch t.vpe, gh'cn by 1~1 . (6.26), IShow
that thc pOS3ible values of k arc given by
of an electron described by the \\,l\"e fune-
k - 2u/,YO , where Ii _ 0, 1, 2. . . . ,.
lion", _ t,k,U(Z) i~
N - l. (b) .\ pply thi~ result, combined
uith Eq. (6.281, to the r-eleclrons in ben-
U'IIC (I<'ig. 5-28) to "how thtlt the IlO".,;iblc
enel1'Y levcL~ lire
\\h erep ...... wSlI dcfined ill ESllmllle 6.-1 and
E.,~ a - {J,
1:".. - a+{J, ltnd E., - (r + 2/J,
whcre the >;{'('oud and third lel"elg arc
.\nalyxe the meaning of each term. ]/lint:
doubly dcg('n('ratc (th e conSltlnis 1:,'." a,
Look at Ta.blc 2- 4 for the operutor co r-
and (J were introd uced in Examille 6.6).
re~llOndin g to thll energy.]
6.2Q l"sing the re~\l l ts of Problem 6.19,
6.l i The cnergy of all clectron ill lin lin
(aJ ~how tlHlt the energy of thc "--elcctrons
iSOtrollic c ry~t:ll ms~' be ('xprc,;s('(1 by
in l)('nU'oc is 6{Ea< - a ) - 8,3 for the
+ +
E - al k; a2k: (rakl, where k., k., grou nd state, ttlld that the first excited
aud k, Are thc CODi llOncnL~ of th(' wavc
~tnt{"< arc ii, 2jJ, :Ind 3P abol"e the ground
nu mber vector I, 1110n/:: the pri ncipal IlXI'S.
Find the (lTcrtivc ma&! along ('ach of the
Coordinate :lX('~ and the cquations of
~tate. (b ) T he 'ir~L two excited ~UtlC!l of
1)(' llz('Il(' corn~'l'ond 10 :I.SeV :HId >l.!I e V.
From an 9.llllly~i~ of the obscrved ('ncrgy
mOlion.
le\"('L~ of benzene, I('rify that iJ i.i aPlJrolli-
6.IS .\lIplying the ""a Ie funr{iOll d('- Illll.\tly 2 e\". On the basi>. of thi~ in forma-
IIcribed in E{I. (6.26) in thl' (,{)ualion for tion. btille whe ther benzcnc i~ n colored
average cllcrg)" ~ho\\" thM Eq. (6.28) is $lIb,t:!.llcc.
 pi

280 Solid,
(considered normal for "chemically pure~
materials). Compute the average distance
between impurity aloms, me~ured in
units of the interatomic distance.
6.30 Very pure germanium used in manu-
facturing &emiconductor devicCll contains
only one part in 109 of impurities which
affect the electrical conductivity. What
is th e average distance between impuritiesr
I'
6.31 When a metallic ribbon, carrying a
current 1, is placed in a magnetic field
perpendicula r to the ribbon, a potential
difference appears between opposite points
281
eJ!icienl.. INolt: In the figure F is the force
exerted by the magnetic field on the charge
carriers.]
6.32 Referring to Problem 6.31, show that
a line joining two pointa at the same
potential on ollposite sides of the ribbon
makes an angle with the direction of the
current given by tan 6 - nql flffi, ,,here <1
is the electrical conductivity of t he ribbon.
6.33 If each atom in metallic gold (density
19.3 X 1()3 kg m - 3) eontributes one elec-
tron to the current, what is the Hall coeffi-
cient for this metal? A thin gold strip
carries a current density of 107 A m- 2 in

-
(lI) ;\r~"li"e ,."rr;rn! fq '"' - .J
F ig u re 6-52
6.21 AS!!uming that the energy of an elec-
tron in a band is given by Eq. (6.28), (a)
find the value of k at which the I'chx:ity of
an cle<:tJ'()n ill maximum, and (b) obtain an
CXI)rCl!o5ion for m- lUI a function of k.
6.22 Plot the velocity and acceleration,
a function of k, of nn electron in the
II-'
third Brillouin zone whose energy is given
by Eq. (6.28).
6.23 ~limatc the I'lldiWl of the Is-elcetron
o rbit in !!Odium (Z - II). Compare this
value with the ('(Iuilibrium dbtllllce be-
tween .!!Odium ions nnd decide whether
such electrons Ill"(' aff~ted in the met:!.!.
6.24 When all impurity alom i~ embedded
in fl semiconductor, we may rw;ume that
the energy Icvcl~ of the impurity atoms
are modified. Verify thnt if E.'I ... is the
ionization cll<'rgy of the isolated impurity
atom, its ionilation energy when embedded
in the &emiconductor is f:, ... - (tO/f )2E;,.t,
where t is the ele<:\ricall){'rmiuivity of the
semicondu ctor. Compute the ioniU,tion
energiCl! of phosphorus (1'), arsenic lAs),
and untilllony (8b), II-hieh are donor im-
purities, when they are embedded in
silicon (8i) (t/ lo - J I.i ) and in gerlllll.-
niulll (Oe) (f / lu - 15.8) . Compare with ex-
perimentll\ re5ulu. l/linl: RcclLll Eqs. (3.4)
and (3.5) and nol(' tlHH in Uydberg's
on the edges of the ribbon (F ig. 6-52).
a transverse magnetic field of 10-2 T.
This is called t he Holl ~.JJtd. Show by
What is t he angular displacement of equi-
referring to the figu re that the direction
potential lines, given that the conductivity
of the potential drop acrOSll the ribbon
of gold is 5 X 1Q7f1-1 m - I ? [/Jilll: Sec
con5t.'lnt we should replace to by e when depends on t he sign of the charge of the
Problems G,31 a nd 6,32.]
parti cle~ ca rrying the current . If e is the
the atom is embedded in a materiaL]
electric fi eld set up by the charges a.ecu- 6.34 In NIlCI, the F-center energy level
6.25 By reference to Problem 6.201 , ana- is 2.65 eV below t he conduction band.
mulated along the edges when equilibrium
lyze what ha ppens to the size of the elec- Wha.t wnvelength does it absorb? What
is established and ffi is the magnetic field,
tronic orbil.!! when an impurity atom is color ill NaCI containing F-centers7
show that RII - eljeB _ l / nq, where j i~
embedded in a semiconductor. At what
the cu rrent density, n tbe number of ear- 6.35 T he energy gap in germanium is
concentration of antimony embedded in
ners per unit volume, and q their charge. about 0.75eV. At \\'hat wavelength does
germanium will appreciable overlapping
The quantity RH is called the /loll tlr germanium begin to absorb light?
between the orbil.!! of the out(!r c\eetrons
of adjacent antimony atoms occur?
6.26 A copper wire with a CrOM l!e(:tion of
IO-~ rn z carries an electric current of
1.5.\. Assuming that there are 5 X IOU
conduction eleetrOI13 per m 3 , determine
the curren t denBily and the electron drift
velocity.
6.27 At room temperature the co nduc-
tivity of silver i116.!4 X 107f1 -t m- I . The
number of conduction electrons ill allproxi-
mately 6 X 10~8 m-3. Estimate the relax-
ation time "T, the Fermi velocity, and the
ma.eroscopic scattering crOIlll section 1:, .
Al;;o find the electron mean frcc [lath,
defined as I. _ 1~ .
6.28 E~timate the conduClivity at room
temperature of NaCI which cont:lins I ppm
(part per million) of divalent calion im-
]lUrities.
6.29 A cubic crystal contnin~ a substitu-
tional impurity in a concentration of 0.1%

7 7.2)
NUCLEAR STRUCTURE
- Therefore we ('annoL speak of a centrlll dominllllL force which oct!! on the particles
, 7. 1 I nlroducliorl
7.2 isotopes, I solones, and i sobars
7.3 The Atomic Mass Unit
7.4 Properties of lhe Nucleus
7.5 Nuc lear Binding Energy
7.6 Nuclear Forces
7.7 The Ground Slale of Ihe Deuteron
7.8 Neutron- Prolon Scattering at Low Energies
7.9 The S hell M odel
7. 10 Nuclear Radialiue Transitions
283
7.1 I ntrtJflu~'l ion
To complete our discussion of the structure of IItomB, we must. now look into the
nucleus of the atom. T he atomic nucleus i!l II. cluster of I)rotolls and neutrons
O('('upyillg fI ,.,mall region fit the center of the atom, with n diameter of the order
of 10-1-1 Ill; that is, about onc len-thousandth the diameter of the atom. Protons
ftlld neutrons arc designated by the common 1lI1lllC of nucleons. Both particles
hfWC spin! Ilnd obey Ule c.xtlusion prinCi l)lc.
When we tomparc the structurc of the nucleus with that of the atom, sc\'cral
n('1I' fcaturesstrike us. In the first place, all the particles that mnke up the nucleus
hllVC practiclIlly !.he same mass, while in atoms the e1ectroms arc very light
e,)mparcd with the nudeu~, For thaL re:\SOll we l!.S.';IIIllOO (in Chupter 3) tJla~ the
'Ic<:trons mo\'oo arQund a nucleus which remaint'(! fixed ill nn inertial frame,
\'omposing thclludeus !I'lld which is produced by 1\ body !It the cenler of the nucleus;
rAther we must imngille all particles moving under their IllUlUIlI interactions. At
nll)~t, a.~ II u~cflll simplification, we mny think of n sort of averflye field of forcc;
i.c., wc mny imagine cach p~lrticJe moving undcr a force resulting fl'om averaging
the fo rces l>rOOlll'ed by the othcr panieles elul'ing theil' motion. In a first approxi-
mat ion, we may considcr this fol'(,c as centm!. I n:~ second approximation, nddi-
tional noncent!'!11 force; may be rC(Luired, This simplified approach has proved
very useful in analyzing nuclear structure.
In the second place, in an atom the electrons possess neg:llive charge and
the nutleus ha.s positive charge, and it is po&<ible to explain electronic motion in
tHms of elcctronmgnetie inter:lctions betwccn the electrolLlJ lind the nucleus.
Hut a nucleus is composed of protons, with positive chnrge, ruld neutrons,
with no charge at alL Therefore wc cannot attribute the stllbility of the nucleus
to electric attraction. On the (:Olllrary, it seems likely that the electric repulsion
betwccn thc protons would scnd thc nucleus flying apart. The merc fact that
nudei composed of protons and neutron!! exist is a dear indic:l.lion of the prcscnce
of another interaction besides the electromagnetic illt{,Tnction, an interaction which
is not dil'Ci!tly related to electric charge!! and \\ hich is much stronger limn electro-
magnetic interaction, T his interaction is called /IIu/tar or strOIlY illttracliOIl. Our
knowledge of the nuclear interaction ill >still incomplete, bllt at least we do know
SOme of its morc importallt characteristic,;,
We identify :I nuclells by the number of protons it has, or its atomic til/mba Z, and
by the total number of particles or Ilucleuns it ha.~, cnlled its ma38/111mber A, Thus
the Ilumb('!' of neut rOlIl' is N = II - Z. T he term Ituclide hus bC{)Ll introduced to
designllte, ill a generic way, all nudei having the Sflm(' Z and iV, nnd hcncc also the
Mille A . I n other wo rds, in the ~:IrI1C W!!y that all !ltoms with thc stl!lIe Z belong
to the@ame element, al! nuclci of the ij!lIllC cOlllpolJition (the same Z and tV) belong
to the s:lmc nuclide. A nuclide is d('!!ignllled by the sy mbol of lhe chemicnl ele-

'84 Nuckar l/rucfurt (7.2

ment. to which it belongs, nc(:ording to the value of Z. with a superscript to the

left indicating the value of the mass number, such M nC, uXa, I07Ag, u'U. S13ble nuclei
Sometimes it is convenient to write the atomic number Z explicitly, in which case o p- emittenl
+ p+ emitters (or electron Clipturc)
a subscript. to the left is added I ~C, nNa, L~~Ag, 2l~u. p+, ~- CJl1itt~rs (o r elcctron capture)
Nuclear force is not 80 discriminating as to require a fixed ratio in the number _j<H!m!llCnl (w, lh P-, P" or electron c<ll)tu re)"!c
of protons and neutrons that can CQe.l(ist. in a nucleus. There CRn be considerable tI <>-<!I\ntters (pure or P-IIt1lble)

flexibility in their grouping. Although there are only 92 natural chemienl elements
(II morc have been produced artificially), there are in the order of 1440 different
known nuclides, some 340 existing in nature and about IlOO produced in the
laboratory. Some of the nuclides (about 280 of them) are stable, but Ii large num-
j~
ber are unstable or radioactive. Figure 7- 1 indicates most of the known nuclides.
The stable nuclei arc indicated by the black squares and the unstable or radio-
active nuclei by the other symbols.
We may observe from the figure that, in light nuclei, neutrons and protons tend
to be in equal numbers (N ... Z), which indicates the independence of the nuclear
interaction from the electric charge. However, in heavier nuclei, the number of
". -1
- ,
'~
neutrons exceeds that of protOIiS (N > Z). There must be an excess of neutrons
"
,,
to produce a stabilizing effect (through nuclear interactions); these extra neutrons
~
balance the disrupting effect of the coulomb repulsion between protons.
Because of the great variety of nuclides, we shall classify them in three cate-
gories: isotopes, isotoncs and isobars.
/801.rype8 arc nuclides having the same number of protons but different numbers
,
;;
Q
of neutrons; therefore they have the same atomic number Z but different neutron <
number N and different mllS8 number A. Since a chemical element is identified ~

by it!! atomic number Z, all isotopes corresponding to a given value of Z belong to

the same element. For example, lH and ~ H arc isotopes of hydrogen. Both
nuclei have Z = I, but IH hM N = 0 and ~H hM N = 1. Isotopes fall along - tV for nucJidC$ lying on this line
vertical lines in Fig. 7- 1.
~~
l~one, are nuclides having the same number of ncutrons N but a different
atomlC number Z (or number of protons), and therefore also a different mllS8

number A. Isotoncs having a given value of N obviously do not all corrcspond to
the same chemical element. F'or example, lie and I~N are isotones. Both nuclei
have N = 7, but carbon hM Z = 6 and nitrogen Z = 7. Isotones fall along hori-
zontallincs in Fig. 7- 1.
Finnlly, iwbara arc Iluclides which have the same total number of nucleons (or
sallle mllS8 number A), but which differ in atomic number Z and lllso in neutron
number N. F~r example, I:C and I;N are isobars, since both have A = 14.
Isobars fall along the 45" lines shown in Fig. 7-1.
Some chemical clements occur in nature with only one variety of nucleus or
isotope. An example is IgF. Others have ilCveral natural iwtopcs, Buch as lin
which has tell, and carbon which has three: l:C, l~e, and 1:0. In addition, four
more isotopes of carbon have been produced artificially. Of all carhan existing in
nature, 98.89% is in the form of I :C. The natural isotopic composition of any Prown number, Z
given chemical clement is fairly uniform throughout the world. Fig. 7_1. Stable and radioactive nuclidell. The 45~ lines are lines of equal mas;! number A.
286 (7.4
- 7.4) Properli(, oj {h( /Iudtu, 287

The analysis of the properties of isotopes, isotone'l, and isobars is important in

that it discloses several features of nuclear 5trtlcturc. Such studies help us, for ' .50' '--~~~-'-''--'--'--'-
example, to predict what will h:\ppcn to the stability of tI nucleus when an extra
neutron or proton is added to it, or to decide which configurations of neutrons and "u 1.2"F~=~i?"'""
protons will be the most stable. ~ 1.00
;,_1.0
, +
.,; .~O.75
7.:J Tilt' ~t'olllie ~'tlJfN IJnil
~ 0.50
~O.1i
When we deal with certain properties of nuclei, we do not need to express the
masses of the nuclei in kilograms. Bnlhcr, in many instances, it is morc' conve- ~
t
e 0.25
nient to usc a special unit called the albmic tIIaM unit (amu), which is equal to
one-twelfth of the mass of the ,~C atom. (Xotc that we say atom find not nucleus,
.~O"o
_ ~~t-*-JL,,-;~~~~.-.
4 Ii 6 7 ij 9 to 0.(0)jo'--'""'3" '-';'!S:'~~7"::~8""':'~OO
nadial di$t.a.nC(>, IO- I~ III lbod"'] d .. t:lnC"C, ]0- 1$ m
Bnd thus this mass unit includes the orbiting electrons.) That is,
(.) (b)
[ amu = ~ X mn.ss of one 12C atom.
Fig. 7-2. (,,) ~ucle:1.r den_ity IIlId (b) chllrjitc den_ity (l~ functions of the rudilll dbtllncc.
(From B. D. n ahn, D. G. Rav enhnll, and R. H of~tll.dter, l'hY8. Rt~. lO t , 1]3] (]956)]
1n terms of kilograms, the vuiue of olle amu is

1 amu = 1.()6O.I X 10- 27

kg. (7.1)
One mole of any substance is by definition il. mass equal 10 1O- 3Af kg (or .ill g)
where M is numeric31ly equal to the ntomic (or molccular) mass of the s ubst:u"H:e
expressed ill runu. A vogndro's constant II' A is the number of atoms (or molecules)
in one mole of any s ubst3nce. Sillce Ihe mass of olle atom (or molecule) is equal
to I.GG<H X 10- 27 AI kg, we conclude that
1O- 3 M 23
NA = 1.0000Ix 10 uM = 6.0225 X 10 mole- I.
Since II' A is independent of AI, the nurnbcr of atoms (or molecules) in one mole is
the same for all !<llhstances.
The mUSlSes given in the ehllrt of nuclides (sec renr inscrt.) arc expressed inalllu.
The alQmic nJ(l$$ of 1111 clement is I he average mass based on the natural isotopic
combination. Thus the atomic mUSlS of carbon is not 12.00000 anlU but 12.01115
amll, due to the presence in Ill\ture of different enrbon isotopes.
By using the relation f; = me', we may express the energy equivalent of one
amu ill terms of joules or electron volts. We leave the student to verify that
1 amu = U.31478 X 10 8 eV = U31.478l\leV,
or about one billion eV ( I GeV).
? .., '"OJH!"tif'ff of tlu' 1\ ' II""'II"
To obtain a clue about the nature of the forces holding protons and neutrons
together in a nucleus, scientists hnve lUlalyzcd BCveral physicnl properties of nu-
clei besides charge and mM!!. We s.hall now review some of these properties.
(I) S i::;c. If we ussume thut a nucleus is spherical, we may exprc;;s its size in
terms of its rndius R. We must, howe\er, uS(' Ihis loncept of nuclcur r:l.diu.~ with
some can'!. We must not pil."ture the nucleus :IS a billiard bnll with a well-defined
surfnce. The value of the radius depends 011 which nuclear property we choose to
determine the radius. The den~ity of Iluclear matter varies wilh the dislallle from
the C<:lIter of the lIucleus, as i"dieMed in Fig. 7-2(a). The density is nPl>roximately
(:on8t[lllt for a considerable distant.-c from the (enter, and then gradually decreases
down to zero ncar the surfllee of the nul"leus. The nuclear radius R may then be
defined n.~ the distance frl)m the Icnter (,f the 1I11eieus itt. whidl the nudear density
hM bocn reduced by OIlC-hlilf. We tall obtain this radius If, for eX:\IllI>le, by
measuring the differellce in energy due to I he coulomb interaction between ndjacent
i~bnrs (i.e., between ioobarie nuclei that differ in Z by one unit) or by flnalyzing
different tYI)CS of uuclear proCCS!lC>i, sut-h as the scattering of (fISt neutrons by
Iluclei. The cxperimentfll rC>'<lllt i~ th:tt Ihe nuclear radius is proportion:!! to 11 113,
where 11 is the mass number of Ihe nucleus. That is,
(7.2)
when'! ro is a constant, Ihe same for nil nuclei. lI S flcrepled vullie is
ro = 1.-1 X IO-L~ m.
It. is u!so possible to determinc the ch:lIgo diSlribution inside II nmlcus nnd from
it estimate thc IllLtlcar radius. Experimcnts with very fast. c\('{:trons nnd muons
SUggest a chargc distribution liS indi('att.'(l in Fig. 7-2(b). The radius of the l"harge
distribution is smaller Ih:1I1 that of Ihe mass distribution, corresponding to a
value
'0 "" 1.2 X IO- u m.
 po
288 Nuckor ,/ruelure (7.4
Some nuclci depart substantially from the spherical shape and must be :\SSumoo
to be ellipsoidal or even pear-l:!hnpcd.
Since the volume of a sphere is 'I1rR 3/3, we conclude from Eel. (7.2) that. the
nuclear volume is
Tout is, rhe I!obwze of a t!11c/CII! i8 proporliollallo the 1IUmber of ttIU:{CDn" II. This
suggcsts that the nucloons arc maintained at fixed avcrllgc distallces, independent
of the number of particles, so that the volume per Ilucleon is a oonSI:mt quantity,
the SfUUC for Illlnuclei. A similar situation exists for molecules in a liquid or in a
solid.
Another conclusion is that nuclear matltr hfU a cons/alii deneily. This may be
seen fI.S follows; The mass of n nucleus of mass number A is apl>roximatc\y
M = 1.60 X 10- 21
11 kg.
Therefore the average density of nuclellr matter is
/II 1.66 X 10- 21 A kg i8 3
P=-y= J.l2x IO UAm3= 1.40XIO kgm- ,
which is independent of A. This densi ty is about 10 16 times greater t.h:m the
density of mat ter in bulk, and gives us an idea. of the degree of compact.ness of
the nucleons in a nucleus. I t also shows tha.t matter in bulk is csscnli:l.lIy ~mpty,
since most. of the mass is concentrated in the nuclei.
(2) A ll g uit, r m o m entum . The resultant. angular momentum of n nucleus is
cnlled (for historical reaoonOi) the nuclear spin. It is des.ignnted by I . Both protons
Rnd neutrons, like elcetrons, have spin 1- In addition , protons lind neutrons
po.'Si!C8.~ orbital angulnr momentum lUIsocinted with their motion in the nucleus.
The resultant nuclear angular momentum (or spin) is oblllined by combining, ill
a proper way, the orbital angular I\omenta llnd the SI)ins of the lludt'()lls com-
posing the nucleus. The nuclear spin is designated by n quantum number 1 such
that the magnitude of the nuclear spi n is h,l1(1 + I). The component of the
nuclear spill in a given direction is given by m,h, where m, = /, (I - I), ... ,
! or 0, del>cnding on whether I is a half-integer or an integer. Therefore there
arc 21 + I possible orientntions of the nuclear spin. As explnined ill Section 3--1,
these sume rules are valid for nil nngulnr momellta ill quantum mechanic",. Ex-
I)erimentlllly lhe values of I arc integers (if tI is even) or half-integers (if .4 is odd)
ranging from zero, lIS in 4He Ilnd 12C, up to 7, as in nOLl!. Table i - I presents
sollle nuclear spins. It has been noted that prnclie;llly nil even-even nuclei (i .e.,
nuclei that have an even number of neutrons and protons) have / = 0, which
indicates that identical lIucleons tend to pnir their ungulllr momenta in opposite
dircetiOlls. This is called the pairing effecl. Even-odd nuclei (i.e., nuclei that have
7.4) Proptrlitl 0/ tk IIU(kw 289
all odd number of either prolons or neutrons) all have half-integrnl IUlgular mo-
menta, und it is reasonable to assume tha~ the nuclear spin coineides with the
angular momentum of the last or unpaired Ilucleon, a result which seems to hold
in mnny cascs. Odd-odd nuclei hnve two unpnired nucleon.s (one neutron and one
pro.ton) and the experimen~al result!:! arc a little more difficult to predict, but
theIr angular momenta nrc mtegcrs, as one would expect., since there is an even
total number of particles. Any theory of nuclear forces, to be satisfactory, must.
account for the experimental values of l.
(3) Mag /le rie dipole fII (Ull etlt. We may recall (see Section 3.G) that a moving
charge possesses an orbital magnetic dipole moment lit I. which is proportional to
its orbita.l angular momentum L and which is given by
M I. = (q/ 2m) L .
For the cnsc of protons, the chnrge is q = e, and therefore
(7.3)
Obviously neutrons have no charge nnd do not have all orbital magnetic dipole
moment.. T he component of the magnetic moment along thc Z-tLxis is
MI.., = (ej2mp)L, = (eh/ 2m.,)m, = ~:-;m"
where the constant
(iA)
is called n. nuclear magneIQ/t.
If the particle has spin S, it may have Ill) additional spin magnetic di l>ole moment
given by
(7.5)
w h~re gs is a constant characteristic of the particle, called the &pi", gyromaglUl~
rall0. - The value for the proton is (ls.P = +5.5855, indicating that M s is parallel
to S (as corresponds to a positive charge). It has been observed that. the neutron
although it has no electric charge, 11a.s a spin magnetic moment corresponding l~
gS.1I = - 3.8263. The negative sign indicates that M s is antiparallc1 to S, lUI cor-
rcsl>onds to a negative charge. These results suggest that the proton and the
neutron have a complex structure which we have not yet been able to determine
exactly.
. We can obtain the resultant magnetic dipole moment of a nucleus by combining,
In a proper way, the magnetic dil>ole moments of all the Ilucleons. Obviously, the
-
rcsultlUlt magnctic dipole moment must. be related to the nuclear spin I. The
.. Reealllbat for the electron Us - - 2.0 (see Section 3.7).
 .,
(7.4 7.4) I)ropulitl of the I!UC~!u 291
29<1 Nucltar Ilrue/we
TAIJLE 7-1 Properl iu o f So",e Nuclidea
rclalion, which is nn extension of Eq. (7.5), is
Electric
Magnetic
Atomic mflS3, quadrul)Qle
:-.'uclide Spin dipole
II-heN:! fit is the nuclear gyromngnctic ratio. T he component of the resultant mag .m" momenl, nm
momenl,
10-28 m2
netic dipole moment of a nucleus along a given directioll lIlay be expressed by
M. = g/(e/2m p) ! .. or since f . = mIA,
(7.6)
:.
:0
IH
1.008665
1.007825
2.014102

I
- 1.9131
2.7927
0.S5i4
0
0
0.00282
~' uclcar nl tlgllclic moment!< IU'C listed as muitil)ies of }lX , and for 1/11 = I. That
is, }l = M .llA s = gi l . .\ ccordingiy the magnetic moments of the proton and
; He
IR
;Re
3.016989
3.016050
4.002603

0
- 2.1275
2.9789
0
0
0
0
neutron (with I = ~) fire }II' "" + 2.7927 nm and !.Ix = - 1.9131 nm. Table 7- 1
gives some vnlue:.s of IA. To be snti!':fac.:tor)', a t heory of nuclear inter!IClions must
i Ll
I!C
7.0 16004 t 3.2563 - 0.045
12.00000 0 0 0
accoulit for 'he observed \'nluCi:! of /J. or gr. ':C
I~N
13.00335
14.00307 I 0.7024
0..1036
0
0.007
(4) Elcdl'ic (/Iuuirul'o/e momf'llt. The electric quadrupole moment of a
charge distribution rela tive to (L given direction designuted t he Z-u:-.:is is defined by
Q' = ~ ,lJi(3l~ - rt>.In the nuclear cu.~c only the protons cOlltribute to lhe
I~N
I ~O
I~O
15.00011
15.99492
16.99913
0
I
- 0.2831
0
- 1.8937
0
- 0.026
electric quadru polc and, Bince qi = e, we get Q' = e Lp (3z~ - r~). ~ormally the ~~Na 20.99395 j - 0.6618 0.093
nuclcar quadrupole is defined as Q = Q'le. Obviously the value of Q depends on nAI 26.98153 ! 3.64'<1 0.15
nCI 34.96885 j 0.8218 - 0.080
the direction of the Z-nxi~. By con venti,)!}, the Z-axis is chosen to be as pnrnllcl
;gCa 39.96200 0 0 0
u.s possible to the nuclear ;<pin I , so that 11"1 / = I. Hence the nuclear c\ectric quud-
rUl)Ole moment is defined by
gCa
~ Fe
42.95878
55.9349 t
0
- 1.3172
1.00

(7.7) ~~Fe
~Co
56.9354
59.9338 , 0.0905
3.8100
In the :\IKSC system, Q is expressed ill m2 . Sometimes a unit called the barn is ;;Cu 62.9296 t 2.2260 -O.ISO
usedj one barn is equal to 10- 28 m 2 Ir the I)rotons nrc distributed with spherical
~:B r 78.9183 t 21000 0.310

symmetry, Q = OJ thus the value of Q is tl good Indication of t he degN)(! to wh ich

nsr 87.0.)601 0 0
~Nb 92.9064 t 6.1670 - 0.220
a lIucleus depaTt$ from the sp\lerical shape. If Q is positi ve, the nucleus must
resemble a prolate ellill8Oid , and if Q is negative, the nucleus must look like an
I~ Rh 102.904S t 0 0
'llCd 113.9034 0 0 0
oblate ellipsoid (Fig. i - 3). It can be shown theoretically that nuclei with I = 0 1:;1 126.9045 ! 2.8080 - 0.790
':!Gd 154.9277 t - 0.2700 1.300
l~tLu
1;~ Lu
174.9409
175.9427
7
2.2300
3. 1800
'.600
8.000
'irLu
1~ 1ff
';~ne
176.9439
179.9468
184.95<H

0
!
2.2400
0
3.1716
5.400

2.6
~~Pb 205.9892 0 0 0
~~Bi 208.9804 ! <1.0802 - 0.3 40
z~L\c 227.0278 I l.l 1.7
~~~U 233.0395 I O.M 3.'
2~~U 235.0439 t 0.35 4.1
(., (" ,,' 2~U
2:!l'u
238.0508
210..1236
0
I
0
- 0.730
0
'.GOO
Fig. 7-3. Cha rge di stribution , sy mmet ri c with respect to the Z-axia: (n) sphere, (b)
I)rols.te ellipsoid, (c) oblate ellipSOid.
 po

292 Nw;kar ,/ruclw e (7.4 7.5) Nm;/(ar bindi'l!) tntrgy

(;3) l'flrily. Kuclcar states have a ccrtnill parity, even 01' odd, dCI)cnding on lhe
'"
str ucture of the wavtl func tions describing the states. Each nuclenr wuve func-
tion dCIX'llds on the wuve function s corresponding to each of the nucleons. Thus
-
the parity of nuclear stnll!!! is very closely reluted to the nucloonic motions. How-
ever, this subject is :1 very {"()mpiicated Olle, on whit'h we shull not elaborate
0.' 6 furt her at present.
odd Z
odd .\'
1':,"" 04.\11' 1.1': i .1. Cnicuilllion of the repulsive llOtenti.11 energy due to co ulomb inter-
action among the protons in 11 nucleus .

0.' , -
Solu tio" , T he elect ri c energy of a homog('neou8ly charged
and TIldill.~ H, i~
~ [lhere, of total charge Q

8 20
'" 50
" '"
Q-
ZR'
Assuming th:n the Z protons in a nlleleu~ arc di!\\Tibutcd uniformly, we may ada])t this
- result by repheing Q by Ze nnd replaeing R by the \'aille give n in Eq. (i .2). Therefore
0.08

, . th e coulomb cncr~y of a nllclcus i~

,

0'"
Introducing nurncrieal ,"/llue;l, In! h:I.\'c
,

..,


(i.S)

0.00



; . Fince the cl{."('lrie charge i.~ not ~1)re:1.I1 uniforml~' vcr the nudellr I'olume but i~ concen-
trated atlhe [lrolon.~, we ~hollld u"e Z{Z - I ) in~tt'ad of Z~ \xo~au\'e eaeh of the X-protons
internct~ ouly IIith the n'l1lllining X I proton~, Thi:l ('Or r('('tion is !':Specially imllOrl:lnt
for nucki '\"lth ~m:l1! Z. ~H"h l\~ hclium, For (,~Illnple, for ~ II ('. IIith Z _ 2 nllli 1 _ 4 ,
,

~

~
-
11'1' h:lv(' Jo."~("'"t1 - D.7i6 :'Ill'\' (ll~in" the ('(,rret'lc,1 formu!:l ), Il1ld for 2~~t:, with Z _ 92
lind ,I - 2;~S, 'I'C ha\"(' H~(<o"11 - 8i!l H eV. \\,(. ,re that bccflU ~e of the Z~ I<rm, lhe
coulomb n'Jlul~;un ('ner"y illl'r\'ll~r~ vcr~' rapully 11111. the nunlh"'r of protoni<. rJlleJ<;! t he

- OJ , nudc3-r imeraclion IS 'tnmg enolL):h and attractive, the !ludeu, cannOL be ~tabl(', We
mu~t com[>l1re the-e eleo:trir energiel wilh those of atom~ tl.nd moleclLl~, which arc of th e
order of 11 few dectron \"olt~. The rea:;on fo r the bil( dIffere nce i~ t hat the protons in a
IlUde\!" art.' much mor" do~ly paek('(l than ('l!'Ctron~ in nil atom, their ><'pnrfltion being
, nbout one hundr('d-thOll~:lndLh a._ much as tho IlV('rage ~elHlruti on of electrons in ntums
20 00
Odd nudeon~
80
S or 1.
100
'" or molecules, TL",uhing in lin ('ncr!Q' roughly 100,000 times greMer.

Fig. 7-4. E lectric quadrullole moments for odd-A n~el~i. T he ordinate, is the unitless 7.:; ."m'I""r Il;,ulin" "'n,ryy
quant ity Q/Z R2, ,,hleb is a better ind icator of the deviatIOn from a spben cai llhapc.
\Ye (':m gl.'t fill ide:. or Ihe ~ I re r lgth of th e I)II('[e:\r interHi."ti(ln by studying t he bind-
ing energy or Iludei: thnl i~, the cller~ r\'tluired to sl'p:\r rtte the nucloons l"om-
or t have Q = 0, a result confirmed experimentally. T able 7- 1 gives the values po;::ing a nudeus. Th(' m :l.~s ur a l1uc1l"u.~ is u]>pr('('iab ly Ies.~ than the :;um uf the
of Q for some nuclei. Figure 7-1 shows the observed electric qundru polc moments mass<.-s of i l:; l"Ollll)(JUelll lI uck'tIll.:<. For example, in the rase of the deut('ron,
of a few nuclei. Kote that some nuclei have abnormally large electric quadrupole II"!d = 2.0 I I J 02 a mu. T he nl:L':"C"S (.If th(' prot 011 ;Ind the neutron arc
moments, indicating very large deformations. Again we say that a theory of
nuclear inte ractions, to be satisfactory, must account for the observed vnlues of Q. I.OOi82.i ilmll and I1In = I .OO8{)(j5 amu.
 ...
.
'
294 ,\ uciror ,truciure (7.5 7.5) Nuckar binding tntrgy

Their sum i~ 111 1, + 111" = 2.0[GI90 :1n1ll, wliidl is larger Ih(1I1 111<.1 by the amount In the la.~~ eXI}rcssion the masses mu s~ be eXI}ressed in amu. Sinee
'"
O.()()?..388 :UllU. The expl:umtion of thi>! ]vs,'I of mn.ss JiCll in the binding energy of
the sy~lcm. m .. + IIt n - 11101 = 0.00"..388 amu,
Consider one proton find one nC\Uron at re<t fll\d ,,;umr.-iently [fir :lpnrt so llml.
the binding energy (lr the deuteron is 1-;6 = 2.22-1 MeV, This is therefore the
there is 110 interaction bctw('(>n thelli. Tlu~ir tuttll encrgy is Ihen the Slim of their
energy required to separate the proton and the neutron in a deuteron, or the energy
rest ma~l!(,";; that is,
rele:\.'!Cd when :\. proton :md II neutron at rest ure combined t.o form the deuteron.
Coml)lIring this energy lI'ith the equivnlenL result for hydrogen, whose ionization
(or bindillg) energy is only 13.6 eV, we conclude tllllt the nuclear interaction is
::\'ow that the 1110 particles arc ('loS(' enough In form a deuteron nucleus
lSUP]><):<C about 10 6 times stronger than electromagnetic interactions. I neidenlally, no
rCl:mlt of thcir l1u('\('(1r intcr:J.ctioll, i,<'t us call Ep their nuclcnT potential
:tS :l. meiL'Sufnble change in mil.SS is observed in chemical renetions becausc the energy
energy. They lHe moving Hbout their ('ClItCI' of m:\.~s :lnd Ihu8 lllsa have some involved in most electromngnetic processes is relatively small, of the order of a
kinctit cIII'rg.v H k . Therefore their Int:l] Clll'rgy i~ /lOW few eV, equivalent to n chnnge in muss of a few billionths of mass units I)er ntom.
:F or :l. nucleus of mass M cOlllposed of II nucleons, of which Z arc protons and
II - Z arc neutrons, the binding energy (i.e., the energy required to scpnrate all
nuclcons) is
But if Ihe Iluclear fOrt,<,!! aTC nltraclivc and the zero of potential energy i~ dlOsen Eb = [Zml' +
(11 - Z)m" - MJc 2
at infillity, /;'p is ncgrttive, All;n, since the deuteron is n !Stable systelll, "-'p IllUSt,
be larger than t:* in absolute value so tlllll l~'* +
6'p i1l negutive (remembel' that
= 931.48[Zm)l + (A - Z)m n - MJ l\-]eV, (7.10)
in the case 'If the hyclrogl'n atom, as well lIS in all bound :<YlitCllls, the total energy, III the sC(:ond expression all masses must be expressed ill amu.
excluding the m:l.'<$ energy, i~ n'g:ttive), Therdore, /:." i!!: s m:tller tJum /::, or in A good indicatioll of the stability of a nucleus is the average binding energy
other wont<, energy is lib('rrtted I\'h('n the system of tl\'O bound nutloo)ls is formed, per nuclooll, E6/ II . It.s vlllue for various nuclei is sholl'lI in Fig. 7--(), One call see
T he energy libernle,J is that it is 1ll!L... imulIl for nuclei in the region of mass number II = 60. Therefore,
if tll'O light, nuclei nrc joined together to form a mediulIl-mass nucleus (n l}roc{"8S
(7.9)

whit'h i~ (,:tiled the bindiltg tllergy of the ~y"t('m, This amount of energy must be
given bad.. to the deuterOIl to separate the ncutron and the proton, We (':In morc
I'c3dily untlerst:md tht'S(' relations if 1\'(, look at. Fig, i,j, The lIuclear binding
energy in the Cllse of the deuteron is the equivalent of the ionization energy in the
case of the hydrogen :It(lm,
En('I'JP' Pl __ T _ T _ _ _ _
infinite liel"llllion
E.
Enel'JP' in __+ _ - ' - _ T__

E-( .. p+on,JC'"
i o
hound state e" - ,",Ie' ;.

"'i~. 'i'-::;, Binding ('nerg.l' or deUleron. '.

! 4

~ 3
] ,
An "dTcctive" mass of the 11-1' system ('un be defined by the relation J~" = 1II,IC 2,
resulting in a value for 111" smaller than III~ 111". +
The binding energy of the
deuteron is then
!'O 100 120 [-If)
,
tOO tSO 200 2'20 210
Eb = (III" + mn)C~ - m,tc 2 = (/lip + IIt n - lII'I)C
2
~[MII number. ,I

= 931.48(ml'+ IIIn - )/ld) MeV, Fig. 7--6. Binding cnergy per nucleon as a function of maSllllumber,
 ..
296 Nuclear slrue/llre (7,5 7.5) Nuclear binding tntf'gy 297

called jU6iun), energy is liberated, and if a heavy !lucleus is divided illto two The origin of this term is related to the pairing energy of nuclei. That is, as a
medium-mass frtlgmcnts (a process cnllcd fissiQn), energy is also liberated. result of the pairing effect mentioned in Section 7.4, the nuclear interaction seems
The fact that the binding energy per nucleon is practically constant (above to depend 011 the relative orientatioll of the angulnr momenta of the nucleons;
A = 10, the variation is only 10%) suggests that each nucleon interacts only therefore the binding energy depends on how many pairs of nucleons have their
with it.s immediate neighbors, independently of the total number of nucloons; angular momenta in opposite directions, or arc paired. This number is relatively
this property is called saillration. This sa(.uration clTect i~ [1150 found in molecules, smaller in odd-odd nuclei and larger in even-even nuclei, resulting in a larger
in which the binding energy of two lltom.!! is prn.ctically independent of the other binding energy for the latter.
atoms in the molecules. The &'l.me situation occurs in liquidlS and solids. The best values of the constants, expressed in MeV, Ill'e
An empirical expression for the binding energy of a nucleus was proposed IIround
1935 by the German physicist C. V. Weisziickcr. As we have indicflted, the bind- a l = IS. 700, a2 = 17.810, 03 = 0.7 11 ,
ing ellergy per Ilucleon i:i flpproxim:llcly constant and therefore the total binding a. = 23.702, o~ = 34.
energy of a nucleus should be proportional to the total number of nu(']eotls or the
mass number A ; that is, r:~ = alA, where al i:i a consltU'lt of proportionlility. It is s uggested that the student check the validity of Eq. (7. ll ) by applyillg it to
However, the lIucleons close to the nuclcar surface lIrC less lightly bound t han several nuclei.
those inside bcc:\Use they hnve fewer neighbors with which to interact. Thus we Note that, from Eq. (7.1O), we may ex])rcss the mass of a nucleus in the form
have to correct our tirst estimnte of r:~ by adding a ncg:nive term. Since thi8 is a
surface effect, the new tcrm must be proportion:11 to the ~q\lare of the nuclear M = Zm" + (A - Z)m n - B~/c2
radius or, in view of Eq. (7.2), pro]}()l"tionallo A 1/3. Thus we may write = Zmp + (A - Z)m n - a'IA + a;A 2/ 3 + a;Z2 A -1/3
t;6 = alA - a2A2/3. + a4(N - Z)2A- 1 - &'. (7. 12)

:\"ext we must consider the rcpulsive coulomb I!nergy of the protun.'!, which nlso The values of the constants appearing in Eq. (7. 12) , when expressed in amu, !Ire
tends to J ecre~e the binding cllergy. From Example 7. 1 we conclude thnt the
coulomb ('orrection must. be ])roporlionai to Z 2A - I /3. Thus we m3y write a~ = l.0!) X 10-', a2 = l.!)1 X 10- 2 ,
H~ = alA - a2.4 2/ 3 - (J3Z2A-I / ". a4 = 2.54 X 10- 2, a~ = 3.0 X 10 - 2.

Another term \\hich tends to de<'rellSC the binding energy is the kinetic encrgy of
the nucleons. As we shall see in Example 13.3, the kinetic energy of the Ilucleons
is prvportiolllil to A +leV - Z)2.1 - '. The first part, which is proportional to .1,
can be included in the alA term. Thus the kinetic energy ('orrection amotLnLs to
adding a term of the form - a~ (N - Z):lA-l, so that
(7. 11)
We can obtain the four const:\nts by fit ling thccquation to the experimental vo.luCli
of E~, which we get by using Eq. (7.10). If \\'1'. chOO'le the constnn ts to flt the
binding energies of nuclei Wilh odd 11 (that is, Z odd and.\' even, or the renrfie),
we find that the binding energy of nuclei with A even fall sy::<tematically on either
side of the valuCli given by Eq. (i . I I ), with even-even nuclei ha.ving :\ lnrgcl" bind-
ing encrgy and odd-o<id nudei haviug a J';mallcr binding encrgy. Thus to obtnin
the best fit of &j. (7.11) for nil nUllei with A > 10, we lldd f\ rorrcctivc tcrm Ii,
such that
EXAMPLE 1.2. Difference in mASS of umirror~ nuclei; i.e., nuclei having the same odd
.-I but with Nand Z interchanged. One pair of mirror nuclei is ~H and I He. Another pair
ia ftNa and nr.lg.
SolUlio", Consider odd-A mirror nuclei which differ by one unit in N and in Z, with
one having (N, Z) And the other (/I' - I, Z + I). Digregarding the pairing energy term
in Eq. (i .12), since II is odd for bolh nuclei, and noting that N - Z - J, 80 that the
kinetic-energy term cancels out, we have
Mz+, - Mz - mp - m.+a31(z+n 2 _ Z2].-t- 1/ 3
mp - !II~ + o3(2Z + I)A-"3.
Actually, since mirror nuclei are light nuclei, with low Z, the coulomb term must be used
with Z(Z - I) instead of Z~, ~ indiCAted in Example 7.1. Thus

, -
r a
,. , -'"
0
_ a ~fl -3/ 4
Z
Evcn
{ Even
Odd
Odd
Even
Odd
Even
Odd
N

I
A
Even
Odd
Even
,uZ+L - Mz - !lip - m.+20ilZ.-I-1I3
(- 1.390+ 1.526Z.-I - 1/ 3 ) X 10-3 amu.

We can usc this equation to obtain OJ from the observed \'alue of the masses of the mirror
nuclei; from the measured I'alue of 0:1, we can obtain the constant TO for the nuclear
radius. It is suggested that the ttudent apply this formula to the two cases mentioned
above.
 ..
(7.6
298 Nuckar ,Irucfurt
EX ,,'MI'LE 7.3. Calculation of the atomic number of the most ~table nucleus for a
given mas& number A.
So/ .. rion: The most stable nucleus with a given mnS!! number A i~ t~at ,whi~h hili! the
ml\:timum value of the binding energy. Thus we havc to e.oml)~te ~t;.JQZ WIth A ~on
stant, and equate it to zero. From the expression for E. gn-en In Eq. (7.11) , and ~mec
N _ Z _ .'l - 2Z, we have that
iJE./OZ __ 2a~!I-I I.t + 4a4(.4 - 2Z) /1-' - 0,
or, introducing the numcrical values of (13 and (1-1 , wc hfll"e
,\ (7.13)
z- 2 + 0.0157,12 13 '
For light nuclei, having sml\lI .1, we on neglect the second term in the d.cnominator, and
we have approximately Z ... lA, a reo;ult confirmed e:tpcrime~tany. It IS 8UggCllted that
the student make l\ plot of Z l\S a lunction 01 ..I up to 2010 (go 10 sleps of 20) and compl\re
with Fig. 7-1.
7.6 l"uele ..r "'ore,'"
1.ct us noll' summarize the main properties of nuclear forces, somc of which we
have already mentioned.
( I) Tile /lude .. r f Qrce is Qf s h Qrt r(J" He. Short range means that the nuclear
force is HllprCl;inble only when the interncting particles arc very close, !lot a sep~
rMion of the order of 10- 1$ m or less. At greater distances the nuclear force. IS
negligible. We IllUY infer that the nuclear force is of short r~nge beca.usc at (~IS
lances grel\ter than 10- 1 -1 m, corresponding to n\lcl e~r dimens.lons: the mteractlo.n
regulating the scuttering of nucleons and the groupmg of atoms lIlto ~olecule:' IS
c1ectromngnctie. I f the nudear force were of long. ran~e, lh.e nuclear mieractlon
bct.wccn the atomic nudei would be fundamental III dl.'!cussmg molecular forma-
lion, dominating the weaker c1ectromngnetic forces in the ~j\I~e wa~ that ~he
c\ectronH1gnetic interaction dominates the even wcaker grnvltatlonal mlernctlon
in the formlilion of atoms and molecules. . '
The range of nuclear forces may be determined directly by Ix;rformmg scutte~~ng
experiments. SUPlIOSe, for exam l)le, that we send a prolon ngalllst. a nuclel~s. I he
proton, on approaching the nucleus, is subject both 10 the electric repulslOn and
the nUl"lear force. 1ft he nuclear fo rce is of a rllnge compArable to .that o~ t~le clec-
trie force, the motion of the prolon , no mntter how dose or how distant It IS II'h~n
it p..'\SSC:!J the nucleus would be IIffected by both types of force and the :mgubu diS-
tribution of the scat;ered protons would differ nppreciably frolll the results for pure
electric (or coulomb) scattering. On the other hllnd, if the range of the nuclear force
is smail, those protons passing at a distance from the nucleus g~ater than the Tl\nge
of the nucieM force essentially experience only a pure eleetnc force .. Only those
protons with enough kinetic energy to overcome the coulo.mb repul.slo~ al~d pass
close to the nucleus lire affected by the lIuclellr force, and thelT scatlenng IS different
7.6) Nurlror forctl 299
from pure coulomb scattering. This latter cnsc is the situation observed eX I)Cri-
mentally, confirmillg the short range of the nuclear force.
(2) Til e "Ile/C(lr fQ rce seeru s / 0 b e i'lde/re,nle,1I Qf e leclri c clwrge. This
means thnt the nuclear interactions betwccn two protons, two neutrons, or one
proton and one ncutron MC b(l.~i c ally the ~ame. For CXaml)le, from the anillysis
of proton-proton :UIJ neutron-prolon scattering, scientists have ooncl uded that
the nuclear part is essentially the smne in both cases. Also the facts th'lt (n) ligM
nuclei" arc COIllI)().';OO of C(lunl num bers of protons il.lld neutrons, (b) the binding
energy per nucleon is approximately constant, and (c) the mass difference of
mirror nuclei (Example 7.2) ClUl be nCCOllnted for by the difference in coulomb
energy nlone, indicute thllt the nlltlcfIr interaction is charge inde[)Cndent. I3e-
cause of this prol)Crty, protons and neutrons arc considered C<luivalent insofar
fIS the lIucletlr fo rce is concerllC(1. For thllt reason, as indicated before, they arc
desigllatcd by thc common IIlUlle of nucleons.
(3) T/,c ,lI/cleClr for cc dCI'C ll.d.~ QII Ill e r c/llti ve Qrie 'I/(lI.iQII of tile spin s oj
L1l e inle rfl c li/l g Iwcie (Jrls. This fact hilS been confirmed by scattering experi-
ments and by analy~is of the nuclear energy levels. It. has been found that the
energy of a two-nucleon sy!!tem in which lhe two nucleons have their 81)ins Ilarallcl
is different frOIll OIC energy of such n system in which olle has spi n IIJ1l1nd the other
dowil . J n fact, the lIeutron-proton sy~lem hilS a bound state, the deu/eroll, in which
the two nucleons have their spins pllrallel (8 = I), but no such bound state seems
to exist if the spins are anliparallcl (8 = 0).
(.1) 'I'll() Iw c ftw r fo r ce is IIQI cQmllle l c/y cfml.r/l / ; il. d e/rCllfis 01/ t.ll e oriell-
talioll Qf tir e spillS re /fltil.:e IQ lir e li,re j o illiliH fi, e fl(:o /llicleQII S. Scien-
tists have concluded t his by noting I hilt even in the simplest nudells (the deuteron),
the orbital :mgu!ar momenlUIll of the two IIlLCleoll~ relative to their center of nl:lSl!
is not (:onstallt, contnlry to the situation when forCC!! are central. Therefore, to
explnin the properties of the ground /ltate of the deuteron, l:Iuch liS the magnetic
dipole and electric quadrulXlle moments, we must usc a linear combinalion of s
(or I = 0) and d (or l = 2) wave fun ctions. Part of the lIudear force seems to be
due to a relatively strong 8pi n-orbit interaction. Another pllrt, clllbl the fCII$or
forct, closcly resembles the interaction betwC<'1l two dipoles.
(5) Tile lIu clcflr fo rce IHI .~ II relml.~ il e core. T llis menns thn~ lit vel'y sholt
d isttlnccs, much sm:llIer than the range, the nuclear force beromcs repulsi\e. This
assumption has heen introduced to explain the wnstant avcrllge s('pllralion of
nucleons, reslIl1ing in a nuclear volume proportionlll to the total number of nu-
elcon!!, as well as to account for certain fClIlurcs of lIuclcon-nue!con scattering.
I n spite of nil thi!! informntion about nudear force.~, the correct expression for
the I>olenti:.l energy for the nuclear interaction between tll"O nucleons is not yet
well known. Several exprCAAions have been proposed. One is the l'ukawa potelltial,
 p

" 300 Nucltar ./tuc/urt

(7.6 7.7) The ground slale oJ Ihe d~ulerO{j 301

7.7 Th e Ground Sinle 01 Ihe Ih!ult'ron

'. f~1'
,,
,, T he deuteron, composed of a proton and a neutron, is the simplest of all nuclei

He,>uLsi\"t rore
,, (if we exclude the trivial case of the nucleus of hydrogen which is fl single proton).
Basically, only the nuclear interaction is operative il\ binding a neutron nnd a
proton together (we may neglect the small magnetic inlffaetion resulting from
,
' p.ulomb potential
their magnetic moments). Therefore, from a detailed analysis of the pro perties
Ilange of '" of the deuteron, we can obtain valuable information about the nature of nuclear
nllc!ellr force , 0
,
.. ~-
of.\----I,';:; forces. The deuteron has only olle stationary stale (which obviously is iUJ ground
0
,, ,, state) with an energy B = - Bb = - 2.224 MeV. Also the spin of the deuteron is
,, ,, I = 1. We may then 8.SSume that Ule protoll and neutroll have their spins parallel
Nlielear potentiaL
,, ,, (that is, S = I) and that the orbital angular momentum of their relative motion
around the center of mass is zero (that is, L = 0), resulting in a state 3S,. In a
1\ ,I state ~1 there is no orbital magnetic moment, and the magnetic moment of the
'-"
+
deuteron should be equal to IIp Il .. = 2.7927 - 1.913 1 = 0.8796 nuclear m ag~
(b) (,) netons, which is very close to the experimental value IJd = 0.8574 lIuclear mag~
(.)
netons. Therefore our assumption about the ground state seems to be well fou nded.
"' ig. 7-7. Empirical shapes for the nu clear potential energy. Considering that the Iluclear fo rces are central, we may express the wave function
of the deuteron in the same form as was done for an electron ill Eq. (3. 18). In an
proposed about 1935 by the J ap::l.Ilc&e physicist Hideki Yukawa, nnd given by s-state the angular part is consllwt (sec Table 3- 5) and we have to consider only
the radial part RCr) = u(r) / r, where u(r) is obtailled from Eq. (3.24). Setting
e- T / . , I = 0 in that equation, which corresponds to a 3S L state, and recalling that m is
Ep(r) = - Er.ro---y-' the red uced m8.SS of the Ilcut ro n~protoll system (Ulat is, m OIl ;mp). we have

where E and '0 arc twO empirical constants. The collstant '0 ill the ran,ge of the fL.2 d 2u
nuclear force and Eo gives the strength of the interaction. The decrclI.8wg CX~ - 2 m. dr2 + b',,(r)u = Bu. (7. >4)
nonlin! factor e.-p/. drops the Yukawa potentio.l energy to zero faster than t e
electric potential energy, which varies as 1/", H~wcvcr, there are c:cn some Let us next, for simplicity, express the nuclear potential encrgy by the square
doubts that the nuclear intl!raction cun be desCribed 11\ ter~llS of n pot~ntl.al cncr~ well represented in Fig. 7- 8(a), which has a depth Bo and a radius a. The problem
function in the same way that we have been able to explam the gravltatlonal an '7, .(")~
ciectromo.gnctic internction9. . b
for most problems the nuclear interac:lion at low eneTgu~s may e
I n any case, . F' 7 - () Beyond
re resented schematically by a potential energy as shown In Ig. - I. a '. .
a ~ertain dis tance the potential energy is practically cons~ant, or (wl:lch IS ~I~:d a " o "
lent.) the force is zero. At. very short. distances a. repulSIve core mIght be .
CF'l 7- 7(b)). This is the type of l:Kltentinl to be included in Schrociinger's equatIon ~i - E.
(b)
!;
wh we discuss n-n and n-p interactions. For p".p iJ~te~actions, however, w~ m~~t
8-
also include the coulomb repUlsion e2/ 41r~or, whIch 15 ImportfUlt. ~nly ?uts, e . e
of the nuclcliT forces (Fig. 7- 7{c)). T he solution of Schrodmger s C(luat l~n
TlInge I t Sometimes to obtain
th gives the stationary states of two-nuc con sys ems. ,
8C~~quantitalive information, one can replace the nuclear l:Kltential by a square Fill _ 7-8. (a) Rectangular deuteron

potential well. h h as we dis-

'0 potential well. (b) Groundstate wave
function.
We cannot discuss nuclear structure with the same t oroug nCS!l
cussed atoms and molecules, since we do not know. the exact f~rm of, the n~c:ear (.)
t~ntial energy to be incorporated in the SchrOd.mger equaholl. N.evert e ess,
~e"knowledge we do have about nuclear forces is sufficient to prOVIde a sound The inclusion of a repulsive core would not substantially change the results we sha!!
obtain in this IICC tion, and for that reason we omit its consideration.
basis for discussing nuclear structure.
 po

,.
(7.7 7.8) i\'t!llroll-proioll lrol/uill!1 at low ttltrgits 30J
302 Nucltar .trudure
The fact that we ha\e to mix 8t:ll~ wi th I~ = 0 :md [, = 2 shows 111:It the orbital
then b(.'('omcs idenlical to that discussed in Example 2.6, sill(."C the Schrodinger
a\lgul:lr 1ll0lllenl\lm of the deu teron docs not have a. well-defincd vullle find thnt
C<luntion for lI(r), Eq. (7.14), is the same:l5 for >/I(x) in thnt c:o.:nmpic. We conclude
therefure the nuc!enr force is \ll)t rigorously centr:l\. 111 the deuteron, the nOll-
thnt the form of I/(r) is celltnll!):trt is nttributed 10 the tellsor force.

11
() _It!
r -
sill k,r,
Ce-a.,
r
r>
< (I ,

(I ,

where
and
a~ = 2mEoIh'.
This wave function is shown in Fig. 7- 8(b), The (:ontinuity of the proper fundion
at r ::: II rC<luircs that Eq. (2.23) hold, namely
k, cot kia = -a
In Qur case we know Eb and lI"e may u ~c this equation to obttlin informnliOIl about
1:.'0 and a. Since there is only one stlLliOlmry state, we retail from Example 2.6
IhM Tr2h~/8111 < Ena 2 < 911" 211'/ 8111. The ground s tate of the deuteron dctcr-
minCII only the value of Eoa' which is nbouL 1.48 X IO-a i\lcV m', To obtain
0 lind a separately, we mu~t hlwe another relation. From scattering experi.
ments we cnll estimate the range a (sec Section i.8). Thus if a is of the om,er of
2 X JO-u Ill, we have that 8 0 is about 37 .:\Ie\', It. mus~ be notcd that. If ~'e
use SOIllC other type of short-range potentinl inste:ui of a square well, we obtmn
difTerent values of Eo rmd 4,
We indiented at the beginning that there is a small discrepancy betwccn the
values of ~<! :1nd ~" +
J.llt which must be :lct'Ountcd for. Also ~Ie deuler,on has ~n
ek'Ctric quadrupole moment Qd = 2,82 X to- 31 m 2 C. But a 'SI Sll\te IS spheriC-
ally symmetric and docs not have l'ln ele<:tric quadrupole moment. Thus we may
su~ pec t thl'lt our !\ssumption of a 3S 1 ground state for the deuteron is not com-
pletely correct.
Another v:lluable source of information :Ihout the 1I11clC:lr force b<:tll'ccll two nu
devn,. i" scattering cxperimel1t~. T o I)edorm proton-proton Stuttering experi-
ment;!, fI beam of protons from :UI :Iccderntor is m:lde to impinge on n target
contuining hyd rogen atoms, :lIId the seuttered !)rOlOIlS arc analyzed. The devia-
tion from pure coulomh SClltlering givcs illforlll:llion ubout the nuclcar force.
Simil:lrly, ill neulroll-proton tiCuuering, a beam of nClitrOIlS from a. IlUde:lr reactor
or other ncutron source is projccted ont o a hydrogen ta rget a.nd the scattered
(7.15) neutrons arc observed . N'eulroIHlcutl'on scattering c."peri mcnts :Ire more diffi-
cult, ~i l1ce it is impo;;sible to hnve:1 tl'lrget l'Omposcd only of neutrons; therefore
some indirect methOlb :11'<: lIeccssnry.
Let 11:S now cOl1sidcl' Il-P .~catleritlg. Su ppose that a bC:\nl of lIeutl'ollS of momen-
tum 7) - hI.: movcs n!ung the Z-axi~, :IS in Fig. (7- 0). TIlliS the incident particle;
mny be described by the wllve function -;". = Cib. The current density cor-
rcsponding to these particles isi;". = IIltf;",,12 = II. Whcn the neutrons pn..."S close
to the t:lrget they fi re subje<:t to t he nuclear forces resulting from thcir interaction
with the protons and are deviated from their initial difC(:tion of motion. The scat-
tered neutrons at a great distflnce from the ttlrget ure represented by 11 wave fUllc
liol1 rCl>Cmbling sphericll! wavCl!; thilt. ii', thcir wuve fundiOl1 hns the form eitrj r
(sec Problem 3.30). The in tensity of the scattering is not necessarily the SillllC in
all dircction!>, :111<1 in gClleml depends on the angle fI which tho di reclion of scat
Incident

--
nNllronil
Now a 3S 1 slate is not the only stale compatible with 13= I. We may_nlso
hnvethestatcs'PI(L= J,S = O),3P.(L= 1,8= I),and 0 1(1.- = 2,S- I)-
I f the vnhlC!! of .I'd and Qd are computed for such s tates, the resuh.s nre all very dif-
ferent from the experimental values, T o solve this dilen,una, ,we may ~um~ that "fT,-*-+-++--z
the wave function of the ground state of the deuteron IS a lmel'lr comblllatioll of
the four possible wave functions we hnve mentioned. But the 3S 1 find 30 1 ~tatcs
hnve evell parity find the Ir 1 find 31'1 stnte!! have odd !>:Irity , Therefore, ~f the
--
ground ti tnte of the deuteron hIlS a well-defi ned parity (1lS is to be e).: ~)ected If the
force is symmetric in the twO interacting particles), we must combme only the
3S , nnt! 30 1 slate!!. A detailed calculation, which will be omitted, shows that to
reproduce the experimental valucs of.u.t and Q~ we m\lst ha.ve
Fig. i-9. Scattering or p:lrticlc.i.
tfdall ...." = 0.98tf('~h) + O.2WeOI)'
 p

." 304 Nuckor ,/rudW'e (7.8 7.<) Neutron-pro/on ualltring al I0o:I ttltrgit. 305

"'00"
tcring makes with the Z-llxis. T hus we may write = f(8)e,k'lr, where f(fJ) is
cnlled the lICatteri'lg amplitude. The tolal wave function is --
'" = 'fine + "'""u
,....
= e"l. + /(8) ~.
, (7.10) -
The flux of particles scattered through the surface dS per unil. time (Fig. 7- 0) is - i-H+- Z
Fig. 7-10. Angular moment.um lones.
--
But dS/ r 2 is !.'Qual to the solid angle dfl subtcndcd by dS. Thus -
Flux of pllrtic1e8 scattered l}Cr unit time through dS = vlf(O) 12 dfl.

The dijJcnmlial crQU sectiOl~ 0"(8) is defined as

O'(IJ) = flux of particles scattered per unit time within flfl
incident particle current dellsity X dfI
~ If(')I' (7.17)
If we observe <1 (8) experimentally, we may obtain /(8) by nppiying Eq. (7.17).
Then we mny look for the nuclear forces which give the observed function f(8).
This provides n meaJlS of guessing the Ilature of the nuclear intcraetion.
Whcn the energy of the incoming neutrons is very low, we may obtain a simple
expression fOI /(8). We note first that the incoming beam is compO.\led of particles
of momentum Ilk, parallel to the Z-axis but moving at dilTerellt distances from the
axis And thus having difTerent angular momentA with respect to the scatterer.
That is, the wave function e;h does not give information about the position of the
particles and we may Sl>cak only of the probability that Il given incoming particle
will have a certain angular momentum. Thus we may say that the wave fun ction
eih describes a beam of particles having the sumo energy lind momentum but dif-
ferent values of angular momentum. In other words, we may express flih ns a
summation of angular momentum wave functions according to
-
only if b ill of the order of the range, or smaller. Thnt is, the only pnrliclC!! which
will be scattered out of the incoming beam are those having l .s
k X range. For
very low energies, k is very small and only pnrtides with I = 0 are scattered. We
say t hen that we have s-scattering. In qUll.ntallangunge we may say thnt ill the
presence of n scnltcrer of short range only the l = 0 part of the wave function
ofi"" ill Eq. (7.18) (or the partial wave ofo) of a beam of very low-energy neutrons
is modified, becomillg f~, while for l > 0 the fI are the same as in J!,c!. (7. 18).
T hus the wave function modified by the scattering must be expressed as
" ~ ,,~ + 2>'
"0
It CRII be shown that the partial wave ofo of zero nngular momentum, corresponding
to the frcc-particle wave fl/n ction oYjoc = eit., is
oY0_- sinkr .
kr
The functiOll krfo = Si ll kr is represented by the dashed line in Fig. 7- 11 (b).

(7.18)
--, ..,. Cain (krHo)

, ,,
where eneh ofl (called a partial wave) eorrcSI)()IIds to a given angular momentum
and lms the sa.me angular dependence as the fun etiolls Y10 of Table 3- 5. (We
0 " " 0
"
,,
,, ,,
must have III, = 0 because, if the particles move parallel to the Z-nxis, their
E! --- ... 'sinh
angl/lar momentum relative to the origin of coordinates must be j>CrJ>cndicular to
the Z-axis; that is l~. = 0.)
Usi ng a cl:UlSielll picture, we mny define the impact para meier b!lS the perpendic- I '0'
ular distance from the Z-nxis whell the particle is still vcry far to the left, so that
L = bp = bilk. But I.. = IIVl(l + I ) "'" III. Therefore bk _ /. Thus, nCl"ording to
their angular momentum, the particles fall within the dilTerent :wnes sho\\'/I in
,.,
Fig. 7- 10. When the IIl/clenr for(.."C is of s hort Tange, there is appreciable scattering Fig. 7-11 . (n) Reelangular deuteron potential well. (b) Positive ellcrgy IVa'c functions.

" . 301i Nuclear a/ruclure (7.8 7.8) NtulrOiI-prolQII ualleriny al /ow enugiu 307 '"
To obiain the modified );ero angular momentum wave fUl1ction .f~, we not.e that. in Obviously Eq. (7.20) corresponds to the case in which the only no nzero phase
the case of u rectangular potcnt.ialll'c11, shown in Fig.o7- I I(a), the particle is free shift is 00. T he phase shifts 01 arc functions of tile energy. By measuring u at
when r> a, but. its wave function for r < a depends on the nucle:lr potential d ifferent energies llnd analyzing the angular distribution of the scattered parti-
energy. T hus the wave function fo r r > a is still a frcc-particle solution, but cles, we may obttlin the 0/" experimentally. 011 t he other hand, we can compute
shifted along the radial direction so that. it joins smoothly with the solution for the 81's theoretically by as.,>uming a rC:lSOnable potential energy fot t he interaction
r < a (recall Example 2.0). We IIlUSt. therefore write between lhe incoming pllrtide llnd the scn.lterer. Therefore scnttering experiments
afe very useful in our seHrch for the form of the nuclear interaction .
1.' _ C sin(1;r + .so)
1"0 - kr .
EXA MPLE 7.,'. Calculation of the cross seelion for S-Scu.ttering.
The (]uantit,y 00 i~ the ph:lSC shift. The wave function 1.:''''0 = C sin (kr 00) is + 5o l ll l ioll: Combining E{IS. (7.16) and (7.18), we m:!.y wri te
represented by the solid line in Fig. i - 1ICb). Note that the lUllplitude of "'0 is
!l1S(l different. from that of f o. T hen it. can be shown (sec Example 7.-1 ) that the
dilTerential scattering cross section is given by
2
0"(8) = sin 00 . (7.10) which, whell compared with Eq. (7.\!1), gives
k'
Since 0"(8) is independent of the angle 8, the scattering i~ spherie:Llly symmetric. e'*'
,
>11o '" "'0+/(8)-
The total scattering cross scdioll is
.,
0"
~
J 0"
(0) dO _
-
411" Sill
/:.2
00 (7.20) From the rCSlllt of Problem 3.18 we know that "'0 = .'\ (sin kr)jr. A more detu.iled analysil;
(which we omit) based on the normalization of the wave function indicates that we must
mak e .1 .., 1/ 1.:. Thlls
because the total solid angle around the iarge~ is 4Jf. From the observed value of
'I"e may obtain the phuse shift 6o experimentally. On the other hand, if one
0" ,
uses Eq. (i .1 5), it e:1Il be shown th:lt at very low energies .,
. f.
- sin kr
-_.
k'
. 2 hk2j2m
Sill 00 = --- . Also, rlS indicated previously in the tcxt,
Eo + E
li enee Eq. (i .20) muy be transformed into '"
'1' 0 -
C sin (kr + 00) .
2 k'
.11I"(h j 2m)
U= Eo+E . (7.21 ) Hcnce we hnve thnt

I n scattering experiment~ the neutron and prolO1: may have their 8pins parallcl C sin (I.:r+ 050) = sill kr +1(9) elk'
(triplet st!lte) or ant ip!ual1cl (;.ingle state) llnd therefore we may determine whether kr kT r
the force is or is not spin-dependent by examining the c]"()~s sect ion in cach ("!lse.
Experimental re,;ult,; show that the two cro.ss sCitions n.re different, thus confirm Recalling that sin a = (e'" - e~i")/2i, after n simple algcbraic manipulation wc obtain
ing the spin-dependellce of the fOIce. The depth und r:tnge fOI the lI"iplct state, thc scattering :!.mplitude s..~
when we assume II S(luare potenlird, h:lve becn found to be Eo = 20.2 :'IleV, iio
(! = 2.25 X 10-
15 Ill, while for the ~inglet slate we must use 80 = li.8 i\JeV 1(8) .. e sill 60.
:lIu.1 a = 2.51 X 10- 15 Ill. k'
A~ the energy of the incominl:l ncutrons incrcuses, the scattering lllTects partial Lsing E:q. (i.li), wc may thcll write the differential ('ross section ll.S
waves of angular momentum ltighcr th!lll zero. The cITed on each partial wave
"'1 is descrihed by II corre~ponding phllSC shift Of, so th!lt the total cross section is 2
,,(0) _ 1/(0)1 2 = si n 00 ,
given by k'
411""" . 2
q = k 2 L.J Sill lil. (7.22)
, which b the e):plcssion given in Eq. (i.H) for I ~ 0 or s-se!lUcring.
 p

308 (7.8 7.8) NtulrOIl.prolOIl l calltring (I//ow entrgiu 309

El imina t ing r2 by using Eq. (7.24), we may write

",lIin'

". To find the dellection of the particle, we must integrate this equation from one extreme
of the path to the other. At.4 the value of to, i~ IeTO because the initial motion is parallel
to the Z-axis, and also I/> - O. At 8 we have II, - ~o si n 8 and 4> - ". ~ 8. Kote that
at 8 the "clocity is again t'O becau.se, by sym metry (or the eon!ICrmtion of energy), the
velocity lost ,,hen the particle approaches 0 must be regained when it re<"l:de.l from O
--z Then

Fig. 7- 12. Coulomb scattering of:\ charged particle.

1,,'"
o
do, - 4
..Ze
rfO"WUV
, ,~
1'~ .
0
81nl/>dt/l

. ..Ze~
EXAMPLE. 7.5. Calculation of the cross I!C(ltion for coulomb scattering of a charged 1108mB - 4 _ ~(I+eosB).
""OIlIVUV
par t icle by a nucleus.

SoI .. /,;OII: When II, charged particle, let us sayan electron, III proton, or an a-par t icle Remem bering that cot!e - ( I + cos 9)/ijin e, we filll\!ly get
(or H(l nucleus), passes ncar a nucleus it cxrericnces an electric force which is rc])ulsiv(l
or attractive depending on the charge of t he incomi ng particle. As n result, the inCQm- (7.25)
ing particle is scattered or deviated from it<! original path. Le t 0 be thl: position of the
nucleus IUld A the initial [>osition of the Ilrojcctilc, very fllr from 0 (Fig. 7- 12). The ini-
tial velocity of the particle, at A, is L'O_ The impact parameter b is the l>erpcndicular dis- This relation gi\'cs the scattering angle in terms of the impact pararneter b or the angular
momentum I. - IIwob.
tance from.'l to a line OZ ]lll$ing through 0 snd parallel to 1:1). Thus when the particle
ill at A, its ,ngular momentum relative to 0 is f~ _ m~ob. If the force is central, the angu- Next we compu te lhe cross 6e(:tion whi ch was defined for the gen('ral case by Eq. (7.17),
lar momentum remains constant during the process. Suppose that a beam of ]Isrticles co ming from an acccleratiug machine is Ilroj('('ted agaiust
Gh'cn that I'O! is the charge of the particle ( .. _ ~ l for electrons, + 1 for protons and a target nucleus O. The particles do not all have t he ~ame augular momentum or impact
deuterons, and + 2 for He nuclei) and Ze is the charge of the nucleus, the repulsive fon::e Ilarameter and therefore they will not all suffer th e o rne deviation. Thotle deviated be-
on the particle is t\\'('('n the angles Band B+ dB are particles hll.\'ing an iml18ct parameter belw('('n /) and
b + db; that i~, the particles falling on lhe shaded riug show n in Fig. 7- 12, which
hILS an area 2rb db. Gi\'en that II' is the number of ]larticlCll per unit cro:ss-sectional area
(7.23) in the incident ocam, then the number of particles p8S.'li ng. per unit time, through the
ring is ro.\" (2rb db ). This is t he same lIS the nu x of 1;C8lteT(.'(1 particles per unit time
Under the action of this force the incoming particle describell a hyperbolic palh, suffering e
within the solid angle dP., defined by and B + dB. The incident curre nt den~ity i~ ob-
a de\'iation (o r !!eRUering) given by the angle 9, which is a function of ro and b, or (which viously rl).\', Therefore, when we apply Eq. (7.17), the t;eallering crOM :;cclion is
is the same) of the energy and angular momentum of the projectile.
When the particle is Ilt any position, suc h as .11, its angular momentum is mr'(dt;/ dl), vo-"(2".b db) b db
ITC (' l - .,'.In
~o . u"
- 2". ....... ,
''''
(7.26)
\.leeall$C r (d<b/ dt) is tho component of the velocity perpendicular to r, Therefore, aince
the IIngular momenluu\ 1I)U.~t remain constant because the force ill central,
where the liu b~ript C stands for coulomb scattering. From Eq. (7.25) , we have

InT
,do
dt - 1Iwob. (7.24)

and therefore
The equation of motion in tho J"-direction is

do . . ..zi.
m""!- f. - F sm4l - - - , sLIl4l.
AI.,
dI 4".tor dfl - 2,.. sin 8 dB - 4". sin;8 cos;9 d8.
 ji2

3/0 I\'llc/wr s/ruc/ure (7.9 7.9) The !htll model 311 "
Substituting lh!'lle values in Eq. (i .26) and using only absolute \'a]u('3, ~incc the n('gali,'c 16() At 6.8 '\leV
l!ign m<,an~ only tlllH 8 Ul'CTCII.!!(,1I when b inCrf~!, we go:>t ' .0 I ~.

(7.27 ) ,',"",,,
3.0
,, , '"I
I ,
Thi~ result ~ho ws that ])(I,rlicles r;cl1ltcroo by tln iUllcr;;e-squ(lrc 1:1.\1' of forc<, arc distributed
stntisticnlly according to a C8C 4 !9Iaw. Equation (7.27) W~ obt:lined by the British
>
,, , ,, 50

'lIltr
" ''''
"

I' r ,I!
physicist Erneot Huthcrford (J!l71- 1037) aud \\':\5 used by him and his collaborators, in { t 28 S2
" ,
2.0 r
,,'" ''
"
c>.:pcrirncnlJl performed during 191 1- 1913, to ansiYlc the scattering of a-psrticlc.~ when the
1l!\rtic\c8 passed through thin roi'~. The e:o.:perimcntai llerHit-alion of the (,>IC~ !e l:Iw JIM- "
:.;,-
,.,, 1" J ,,(\r \ "" ..1:., ,'
,,"",, ,.. '''
,,'".,,,
vided the cllidcm,:e for the nuclesr model of the stom, which h~ been !l.!'ecptcd ~ince then ,I I ' \~I \
"
us the r.o''rect atomic model. 1.0 I , , ,'
If the only force e...:crtcd by the target nucleus on thc proje-ctile is the co nlomh repul- 20 ' ... _ / \ ,
,......... __ . / , ,, ''
.'
,, , ''
sion, Eq. (7.27) would hold Ilt all tnergies. Bu~ when the proj~tile hILS an aogul:l.r mo- \
mentum (or imj)aCL j}3r:lmeter) s.mall enough and an CIICrg)' high eoouJl;h so Ihs L thc \ ,, \

projectile pss.ws very dose to Ihe nuclcus, deviations from ad") Inay ari~e if a short-
ranRC nuc!car force ('xists in addi ti on to the coulomb force. From the nllslysis of theso
dcviil.tions, we m:l)' compute the phnse 8hift~ for the nuc!elr effects. ThC!!o eoml)utalions
provide information, for e);alllllle, sbout the nurlear force betw(l('n t\\"o protons.
\\"hell the projectiles Me ell(rgetie c!ectrons, they may pelletmte through the nucleus.
Thi.s sl:lO introduces n deviation from ad"), which in this cs~ is due 10 the eh:l.rge djj.
Iributioll within the nucleus. From the :lnfllYllis of theS<l deviations, the curvC!! shown in
Fig. i~ 2 wcre oht:linc(\ by R. l\ofst adter and his COlillborMorl\.
:\"01(' Ihnt, in tho abo,c di;;eu,,~ioll, we have u$Cc\ II e1a.s..~ical description of the coulomb
seanering which may seem an uncalled-for dcparture from the Ilfocedure for describing
nuclear scattering in the preceding !!CClion. However, IlIl1.thelllllticlIl calculations of co u-
lomb senttering using quan tal !Il('\h()d~ are rather invoked (l.ud b<>yond th e ~c()pe of thi~
book. One rcru;on for Ihis ditlit;ulty i3 that the coulomb for~e, gh'cn by Gq. (7.23), is of
long range and th erefore affects all plIrtial wa,C!! in E:q. (7.18), evcn if the energy is very
low. On the other hand, coulomb .scattering i,l one of tht case~ in which the ela....,icll.1
and quanllli dcseription~ agrec in their rC!!ull~. I t can be shown IhM the 1!C:'Itleriug
amplitude for coulomb l!Catterinlt i~ given by
/c(")
which, when substituted in Eq. (i. li), gh'es tho same value of (1e as Eq. (i.2i) . In thc
aoo,'c l'<lu(ltion, l' - ~lC2 btofil'O :Iud 1)0 i~ 'I corhtant which dC[lend~ 011 'Y.
A bl\.~i(
goal (jf nuclcnr phpi('S i~ to determine tho motion of the llucleons in n
I\udcu~, ,md from the motion 10 deri\e nlH-it'llf properlie:<, both in the ground :lnd
the e"dted ".t:lt{'.~. The problem ii more 1\,ml)Ie.'( thall ill th e atomic 1:l$e, due to
th(' l:Iek of a dOl\lillanll"eJltnll furlc nml the exi;;tclwc of t\\'o d:l.~~c>l of parI idcs-
nel1tr"'m~ and \lr"tnll~ e,l("h da~s l;e ]>atatcly obeying the e);clusiun prindple.
'- -"" '''--
0
'w
W
" 00 80
Number of neu!ro"~,.v ''' '" ''''
Fig. 7~1 3. Energy of the finn excited st:lte for e\"en-cven nuclei.
However, there is strong evidence indicating th at each nucleon mo,'CS in lin aver-
age field of force which is produced by the other nuc100ns and whidl, in Ii first
approximlltion, may be considered central. Thus, using all independent-particle
modelns we did for the electrons in an atom, we should charllcterize the lIudeon
energy s la tes by quantum numbers I~ Ilnd /, giving the energy level and the orbit>ll
angular momentum. Quantum number /I is chO!!ClI to label the order of inc reasing
energy in which successive levels with the srunc I fi ])pcar. Thus Is, 25, 35, ... , etc.
mean the first, SCC()lId, third, and so on, levels, nil with I = 0, ill order of illcreasing
energy.
In the MlI1C way t.hnt. atoms exhibit. /l. shell st ructure, alld have eomplcte shells
wh en all occupied energy levels have their full quutn of electrons, nuclear levels
(i .28)
also e.-.:hibit a s hell-like stru ctu re. Since there nrc two classes: o f particles in n nu-
cleus, there i.'!l II. d ouble-shell arrangement, one for protons :\nd another for lIeul rons.
A~ cer tain valucti of Z or N corres]>onding to complete shells, llUdei result which nre
particul:lrly stnble, in the same way that iner t gases consist of atoms with ccrtain
L"Omplete c1<x:tronic shells. These values of Z or tV (commonly called "magic
numbers~) arc 2, S, 20, 28, ;;0, 82 and 126. For example, Fig. 7- 13 shows the
energy of the first excited state of several even-evcn nudei. ~Ingie-number nuclei
show an ll.bnormally high first e);citation energy, suggesting that, nt the magic
numbers there is a hllge energy gll.p belween the last filled energy level or shcll and
tl~e next empty s t:lte. This is also thc (':\.5C for the Moms of inert giISCS (recall
Frg. 4-5). Similarly, the number of stable isotopes and isotollcs with Z or N C(jual
to a magic-number, res pectively, is rellltivcly large (F ig. 7- 1'1). Also th e neutron
 pi

, ,~,

JI2 (7.9 7.9) Tht ,htll model 3/3

10.000
@ @@ @J @
I I I I I
barns
1\uJlci of ~,.~" '" on ly

""" , ,,.
.~ 100
'" "I '" I ~
Number
of .table
itolopft\ i
~ 0
Z-=--.OO

V' 1\
.'

, IV

. (J.
.~
Number of prolollll, Z

@ @ @ @J @ o., !
I I I I I
" '" 30 liO 70 SO
I'Ufnl.ot:r of 1\CUlrotl~
00

Fig. 7-15. Cross section for neutron ca pture as a function of the number of neutrons.
"Xl "0
'''' ''''
[,\ dapted from B. FloWCTll, Prog. in NIIC. PhV~ic. 2, 235 (1052): London: Pergamon Press]
Number
of stable
itotonfll levels by the spin-orbit interaction, with the lower energy corresponding to L and
5 parallel. Thus a nucleon energy state is characterized by the quantum numbers
1'1, I, j, where j = l ;. For a given I, the state having j = l + ; has lower
energy than the state with j = l - ; . This is contrary to the electronic case in
atoms, and shows that the nuclear spin-orbit interaction cannot be of c1cetro-
magnetic origin. Since
L 5 = j-(j2 _ L 2 _ 52)
Number of netllronsV
~ W(j+ 1) - 1(1 + 1) - tlh'
Fig. 7-14. Number of ~table nuclides as a function of (a) the atomic number, (b) the
neutron nu mber. i - I + t.
j = / - ;,

capture cross section of nuclei with magic-number N is extremely low (Fig. 7-15), the separation between two states with the Slime I but difTerent j is prol)Orlional
indicating a very weak binding of the extra nucleon. to 2l + I, and therefore increases with I. The degeneracy of each n, /, j state is
To explain the valuC.'! of the magic numbers, 1\1. G. Mayer and J . H. D. J ensen 2j + J, corresponding to the 2j + J possible orientations of J relative to a given
proposed independently in 1949 that, in addition to the ~veragc central fore~, axis. T hus, according to the exclusion print'iple, the maximum number or neutrons
there is a strong spin-Qrbil interaction in nuclei (not necessarily of electromagnetic or protons in a given 11, I, j levcl or shell i~ 2j + J; lIlfl.t. is.
origin, as in the case of the atomic electrons discussed in S~ction 3.9) whi.ch n.c~B
on each nueleon and which is proportional to L . 5. T he eXistence of a apm-orblt j
interaction is amply supported by experimental evidence (see note at end of this
section). Since 5 can be either parallel or antiparnllel to L , giving difTerent values number of
;\111:":.
2 4 6 8 10 12 14
of the total angular momentum J = L + 5, each (n, l) level is separated into two protong or neutron~
 .. ..
,_. ..
(7.9
7.9) 315
314 Nuc/mr liruclurt

j splitting. The slight difTeTCnce betwccn proton and neutron leveLi is due to the
" coulomb repulsion betwccn the protons. Several empirical centrnl force I>otentiab
T otal nnmh!'r
or nucioornl "'i;;;;;;;;! have been proposed to reproduce the experimental ordering of the levels, hut none
hIlS yet a full theoretical and experimelltal basis.

'~---;:;kr------------:~r------~r
It has been observed that atl even-cven nuclei have zero s pin in their ground
state, while in odd-A nuclei, having Z even and N odd (or the reverse), the nuclCilr
~pin I coincides witJI the j-value of the Inst odd Ilucleon state in most cases (in a
few C:\SCS it is equal to j - I ). If the odd nucleon of flll odd.1 !Iucleus is excited
to a nearby state, the nucleAr spin of the excited state generally coincides with the
2r--<: 2r_: new j-value of the excited nucleoll. Bellce, whcll nn (n, f, )) level is being filled, it
seems that identical nueleollS pair thei r lotal angular momenta so that if the

~---d------~r-------------t ------~:
number of identicnl nucleons in the ('1, /, J) state (protons or neutrons) is even,
their rcs\litnnt angular momentum is zero, and if it ill odd, their resultant angular
momentum is j (or j - 1). For odd ..odd nuclei (of which there are only fou r
stable ones), it is more dimcult. to determine the nuclear spin, and all integral
+
values of I from j~ jn to Up - jRI are allowed in princi ple, whcre j" corresl>om[s

oo---;:~---m~r------m---~:~ ------~:
28 ___ ~r__ ------f------ -- --- - - ---l~~-----T---
W--------------------------------------------
to the unpnired proton and jn to the unpaired neu t rOIl. In certain cases the largl..'St
possible vnlue of I is prefcrred and in others the smalles t..
An independent.. particle shell modcl cannot uccount for these coupling or Iluiring
rules of the angular momenta of the lluo:;loom~. These rules are n.ttributed to
t he so-called "residual" intcraction, i.e., the difTcrcnee bet.wccn the actualnuc1car
interaction experienced by II. nucleon and the llVcrage central plus spin--orbit force

-~.
I
~d-< It
I
"-<
2s t1
introduced in the shell model. The rcsiduul iHtcfllction I..'()ntri butes to the nuclear
stllbility by what is called (I pairillg--cllcrgy effecl. We can scc this stabilizing efTeet
from Table 7- 2, which shows the number of difTcren t lY I>CS of stable and almost
!ltable (or long.. lived) Iluclides. There is nn obvious nmjority of s table evcn--cven
8-------------1
II~ I
------------------------------
IV-<: nuclidcs.
T ABI, E 7-2 N umbe r or S tab le a nd Ve ry
Lo"S .. l.i ...:d Nucl ides
" - - -I ',----1
Z N Stable Long-lived

Fig. 7- 16. J>roton and neutron energy lc\'clil in the shell model. [Adapted from P. F. A.
Even
Evcn
E vc n
Odd
15'
53
11
3
Kl inkenberg, Hm. Mod. PhY3. 2-1, 63 ( 19.52)]

As for the ntomic electrons, each nucleon state is designated by the letters s, p, d,
Odd
Odd
Evcn
Odd
50
,
3

etc., corresponding to the vnluc of l, and a subscript giving the value of j. Thus
The shell Jllodcl has bl..'Cn ruther sllcecs.<lful in predicting many properties of
for l = 0 we haye nn 8 1/2 state, for l = 1 we have states Pl/~ [lnd 1>3/2. for I = 2
n(lClelir s tates. In some instances rather clabofllte cnlculations are required. H ow..
the states are d 312 nnd d $/2' lind so on.
T he Ill'rangcmcnt of s ingle-particlo energy levels for protons and neulron$ b ever, in lllflll)' cases the s hell-model ca lcullLti o n ~ fflil to explain the cx-perimental
facts accurately. For ex-ample, electric qundrul>olc moments calculated using the
shown schematically in Fig. 7- 16, which indicates how cach (n, I) levcl, due to the
shell model are eOllSistently 100 small, C!' pecially ill the regions between magic
avel"lIgc central force, is spli~ by the spin-orbit interaction. T he parity of each
numbers or closed shells.
level is given by (- I )'. The ordering of levels follows the rcquiremen ts of Ihe
experimental evidence. T he energy gaps at. the magic numiX'rs nrc clearly shown. Because of the strong coupling :\mong the nucleons, there are seveflll coliecti~'e
effects in 1\ nucleus. 1\ucleons occupying the core, com l>osed of I..'() mplete shells,
They occur every time a ncw high value of I nppears, producing a large s pill-orbi~
 pi

J/9 Nud~r IIrue/ure (7.9 7.10) .Y!lrI~r rariiali!)t /ra,"ili()l16 319
;
,
magnet ic moments do ML lie on eith<'r of the Schmidt IinC:! but in the I"<'gion between

-
them. The lack of precise a~recm<,nl is not surpri~ing , ."ince the ind<']lend<,nt-particle
, shell modcl ilia mther crud<, onc. If ono u<;('s the unified model of the nucleus, it is possible
to obtain n better agreement.
,
,
,,
0
3 ' 11 0
.....
-
~
;;~

- , j - I-t
In llddition to the ground-state (onfiguratiun, a nucleus lIlay have scveml excited
stntes. These may be classified into two groups: particle excitatiml4 and collcclitoe
excitatioll.!. In a particle e:o;:citation, olle or more nudcons arc shifted to another
levd of higher energy without CSS<'ntinlly modifying the motion of th e other nu-
0
-. cleOli!!. Particle excitation ell('rgies nre of the ord('r of one .'ole\'.
-, A!! ('xpl;\ined in the pre\ious !!l'<"tion, l1ucl<"i which arc in r<'gio!!>! f:lr from magic
! ! I ! ! numbers and which have inc~,m l)leldy filled s lt!:'lIs are not. s ph<'ri<,al, but rCS<!mble
j-I prolate or oblate elli psoids. Jn t hesc deformed nuclei, as in moIc<'tlfes, the prineipni
a.~C8 rotnte in space, rcsulting ill :\ collceth,t rofulion in which :\llllll<,lcons partici-'
Fig. 7-18 . .'ohgnelie dipole moments and Schmidt lines for nuclei wi lh odd Z. patc. T he rotational Cl!<,rgy i~ qu:mtiuxi, and therefore tI dcfol"lllCd nuclells has
scveml rOtation:11 encrgy level;.. Fur cyen-eVcn nudci, the rotatiorml encrgy levels
are given by

,
j-I-t "
Brat = 2iI /(1 + I), (7.33)

where I is the :lIlgular rnom<'utum of rotation o f the whole tludeu!!, which, for

,
:;
symmetry r('asons, <'all take only ev('n values; that is. 1 = 0, 2, -I , . Therefore
all rotntiormllevels have ('\'('11 parity. The effective moment of inertia uf the nu-

,
0
0
cleus isS, nnd it is always I<'AA thnn the m()-
mcnt of incrtia which we obt ain Ilhcn we , k~V

-,
, CQm;iticr the l1ueleu~ as a rigid ellip~oid, be-
cause nQ~ all lluclcOH$ pa rticipate in the
'-- - li"1S5
"--50'
"
> 8lIme wfly in the rotational motion. Fig-
ure 7- 20 ",how$ the rotational ('rlel'gy lel<,11<
for rt n f :lnd 238Pu. The!'oC ('Ilerg..r
- 3 .311e lo'cls cleMly follow th(' pattern giv<,n by
Eft. (7.33). For nuc lei olh<'r than CI'<'Ii-(!'en
I I I ! I ones, the arrangement of rotation:\1 I(',els '-- - &11.7
i-I '- - - 303.;
is more complex.
"' ig . 7-1 9. ,\Iagnetic dipole Inoments lind Sehmidllines for nuclei lI'ith odd ,V.

In tho independent-p:l.rIicle ~hell model lI"e have that, for odd .4, tho nuclear spill i.s " - - 300.3 -,---146.0
considered equal to the nngulflr momentum of tho unpaired particle. Therefore, ~etting
I _ j in Eqs. (7.32) :lnd introducing lhe value~ of fir and fl. for protons and neutrons, lI"e
obtain two sets of values for ,"" dependin g on whethe r Z or N is odd, as a function of the
nuclear spin. These arc elllled Sc/rmidt linn; they are represented in I~igs. 7- \ 8 nnd 7-\!) '---93.3 3 ' - - H.tl
for odd Z llnd odd X, respectively. The II.Ctual e:o;:pcrimentlll values are indicated by Fig. 7-20. n otationsl en<'rgy Ie\"eI~ of lsollf O' ----0 0'----0
crossett for j - 1+ ! and by eircle$ for j _ I -!. We can sec that m~t of the and 2381'u.
~ ""
J>(t EH
 pi

Nuclear Ilruclurt (7.10 7.10) Nuclear r(ldi(Jti~ v(lrI.li/ionl 321

In addition, there mny be several vibrational excited states a.ssociated with the k,V k,V k,V
collective oscillations mentioned in the ])receding section. These excited vibra- ,r (to i)~ 722 ,- ,...
tionnl states are separated by the same energy Aw, where w is the vibrational "',r '"
300
angular frequency. For even-even nuclei the rcsultant spin or angular momentum
d!' I (tori)' 637
0' J H'"
of the fi rst exllited vibrational state ha.s a value of 2, and the second excited vibra-
t ional stil.te may have a spin of 0, 2, or 4. Doth levels have even parity. Ifigure 7- 21
""
shows some vibrational levels of uJ\r, 12&'I'e, 136Xe and 1~2 pt. Both collective dj' 247
rotational and vibrational excitation energies are in general much less than par-
ticle excitation energies, and amount to a few keY. This tlCCOunlS for the low-
dj'
-rr--++'" ,'--'C,--L.U 90
lying first excited levels of highly deformed nuclei which lie between magie-number
nuciei, a.s showll in Fig. 7- 13.
.,,- 163
"
-\' SO

3'
,- oj' 0 W
I 0 0' 0
'.lied 'liXe J~Xe

, " " Fig. 7-22. Radiative 1'-transitions of JUCd, J~~Xe, and I~Xe
"
of the motion of the nucleons in a transition between two nuclear stAtionary
states. Some 'Y -Iraru!itions of IUCd, 1:~Xe, and J~~Xe are shown ill Fig. 7- 22.
--,-'---- ~--~- -~----,-'- The angulnr momentum and parity of each level is given on the ldt and the energy
of cach level relative to the ground state appears on the right.
Although, in atoms and molecules, only electric dipole transitions are important,
O' Or o' o' o' higher electric and mngnetic multipole transitions arc often important in nuclei,
o ,.,;;;:;;ti~--- 52". -- J2>IITe -- 13O)Xe -- IJrl I't
llCheme especially in collective transitiOlls in which many lIucleons participate. Electric
llIld magnetic transitions aTe designated by the symbol E or M followed by the
fig. 1-21. Vibrational cnergy leveJ.s of some nuclei. numeral 1,2,3, ... giving the value of tJ.{ and corresponding to dipole, quadrupole,
octupole, etc., radiation. The type of transition is determined by the chAnge ir.
Kuciei which have complete shells arc spherical, and do not e:\;:hibit low-lying angular momentum and in pJlrity of the Jlucleus, according to the following scheme:
rotational or vibrational IcveLs. Nuclei with almosl.-oomplete shells arc only
slightly deformed, and do not exhibit rotational excited levels but only vibra- Spin
tionallevels. From our discussion we see thAt the energy levels of a nucieus are change Af - It - I ,. 1 2 3
ns complex ns those of a molecule. However, to theoretically predict the energy
levcls of A nucleus is morc difficult than to predict t.hose of a molecule because of Parity y~ El M2 3 l\14
our incomplete knowledge of the nuclear interaction. change No l\1l E2 :'-13 E4
A nucleus muy be carried to an excited energy level when it absorbs a photon
of the proper energy or when it undergoes an inelastic collision with a nearby pass-
ing fnst I)articlc, such l\S a proton or a neutron. If the l)arlic\e is charged, this Radiative transition probabilities depend on the energy difference betwCt:!n the
!aLter procCSll is called coulomb eIcitation; it is very uscful for studying the low- two states involved, the Jll[ISS number of the nuclells, and the spin change. The
iying energy levels of deformed nuclei. transition probability increases ns the cnergy change increases and decrellSCS as
An excited nucleus may give off its excess energy and undergo a transition to the vaiue of III increases. Therefore, for a given energy chAnge, the iarger the dif~
the ground levcl with emission of electromagnetic radiation, called, for historical ference in angular momentum between an excited stale and tile ground state, the
reasons, gamma roys. T hus the nuelear ga.mma-ray spectrum is similar ill origin lower the transition probability and tile longer the lifctime of thc e.xcited Slate,
to atomic and molecular spectra. The l'-spectrulll results from the readjustment unlcss there is the possibilit.y of a tmnsilion to another excited state of lower


322 Nuclear l/rUc/urt (7.W

Nllckar radiali~ {rami/Will
7. 10)

". ' , ,

JP 2.6 min MeV

,,--""-T""-O.66t
1010
- "
'''' t- ---
-
" . ''''
0t- -

------------
-----
,- - - ; ; ; ; ; - - 0
mnn
02" t- / -

,-.,
(.)
10-
10
~--- ___.\I!

------
11 100
El ---------- __
------ [p .\lcV
J
lO- lS' ---------;cb---------;;! !- T'~ mi.. 0,"'
t-
- -
Ii I~ !~
f: , keY 00
Fig. 7-23. Lifetimes for i!illgle-pllrtic\e transitions involving !I. proton for !I. nucleus with
mass number npproximntely 100, 8ij llredictcd by the shell model. i~ 0.009 "'t-
:'111
"" 020'" '"
0
energy with a smaller change in angular momentum. Figure 7- 23 S?OWS the li~~
times of excited states, lIS a function of the energy absorbed or emItted, for dif-
! !l3 Kr

(h)
O
20 " nucleons,
Odd
00 SO

ferent mullipole transitions involving a proton, calculated using the shell model,
for a nueleus with mass number about 100.
Collective rotational and vibrational transitions, which have d[ = 2 (and no
change of parity), are of tYI>C E2, or electric quadrupole transitions. Obsc:-:ed
electric quadmpole transitions in many nuclei with unfilled shells have transl~lo.n
probabilities that are larger than the values predicted by the shell model. 1 hIS
suggests a rather large electric quadrupole moment for these nuelei as compared
with shell-model calculations, and hence a relatively large deformation (recall
Fig. 7--4). It was this fact which gave the initial impetus to the collective model
of the nucleus.
From Fig. 7- 16, we can see that in odd-A nuclei having Z or N slightly less than
the magic numbers SO, 82, or 126, there are nearby energy levels which difTer
greatly in angular momentum. This gives rise to excited states having relatively
long lifetimes. For example, in 1371h (Z = 56 and N = 81), which has one neu-
t ron less than the magic number 82, the odd neutron may be either in the 2d~ 12'
3S I / 2 or Ihll/2 slates. Actually the ground state corresponds to the configuratIOn
in which the odd neutron is in stale 2<13/2 and Lhe nex~ excited stale corresponds
to a configuration in which the odd neutron is in state Ihll/2 (Fig. 7- 24 (a. The
difference in energy of the two states is 0.661 MeV. A transition between the two
. N or . Z -
Fig.7-2-~. Isomeric tl1lnsitions in Fig. 7-25. Longlived isomers of odd tl . IAdapted
137& and 83Kr. from M. Goldhabcr and R. O. Hill, Rev, . .1100.
Phy" 21, li9 ( 1952)1
8tatescorresponds to to! = 4 and a change in parity, and thus is an ) 14 transition.
T he observed lifetime of the excited Slate is about 2.6 min. Another example is
831\r (Z = 36 and N = 47). This nucleus hn., three neutrons less than magic
number 50. The states competing for the ground-state configuration arc 2Pt l2
and Ig ol2 . The first state has spin; and odd pariLY. T he second configuration
could have spin t or! with even pariLy, giving rise to the energy levels shown in
Fig.7- 24 (b). T he observed transition is , = t- --+ ! = ;+ rmd is fln E3 transi-
tion with an energy of 0.032 1\lc". The lifetime of the! "'" ; state is about. 114 min.
Kuclei which are in excited statc!; alld which have n reLlsonably IOllg lifetime are
called isomers. T ransitions for which to! > 3 :Ire designated :~ i.wmcric transitions.
Figure 7- 25 ShOII'S the distribllLion of nudei having isomeric statc!;. They appear
in groups cl1lled islallds of iSOIl!UISII!, which f:\11 just. bdow the magic numbers,
according to the predictions of the shell model. In fact, the explanation of
these islands of isomerism i~ one of the succC!\Ses of the l<hell model.
 p

Nuclear ,/ruclurt Problmu 325

7.9 The interaction between the electron Compare thi.!! encrgy with the difference
and the nuclear magnetic moments gives in the binding cnergies of 3H and aBe.
I. "The Nuclear Force,~ It Marshak, &i. Am., 1'olarch 1960, page 98 rise to a hyperfint ,pWling of the atomic Is the result co mpatible with the assump-
2. ~Nuelcar Models, ~ It \'an Wageningen, tim. J. Phy . 28, 425 (1960) energy le\'els. The energy due to this inter- tion that nu clear forces are charge inde-
action is Ilrol)()rtional to llende nt 1
3. "Pauli and Nuclear Sllin," S. Goudsmit, Ph"ric. Toda", June 1961 , Ilage 18
7.1 ' 1I0\\" much ellerg.y is required to re-
4. "The Nucleus Today," D. Bromley, ThlJ Phyricl Teachtr 2, 260 and 320 (1964) move (a) a proton and (b) a neutron from
6. "Problem of Nuclear Structure," V. Weil!.skopf, Phyric. Toda", July 1961, page 18 100 and from 1701 Is thc TeIIuh an indica-
where' is the distance of the electron from
6. Nudtar Foret., D. Brink. New York: Pergamon Press, 196.5 tion of the existence of pairing forces?
the lIucleus. Show Ihat the hyperfine split-
7. Structurt of .4 tolllU: Nue/ri, C. Cook. New York: Van Nostrand, :'.Iomentum-Books, ting is of the order of 10- 5 eV in energy, 7.15 }I' rom the atomic masses given in
190' givillg rise to a hyperfine st ru cture of spec- Table 7- 1, calculate the lotal binding
tral lines which is of the order of 10- 2 A energy and the binding energy ]ler nucleon
8. Strudure of Matter, W. Finkclnburg. New York: Academic Press, 1964, Chapler 5, for 1Li, 160, ~7 }1'e, and 17GLu.
Sections \-8 when the lines are in the visible range.
7. J6 The empirical Weis.:1cker formula,
9. Poundation, of Modern PI!ytical Scienct, G. Holton and D. H. D. Roller. Heading, 7.10 The hyperfine splitting of atomic
E\]. (7. t 1), cOUiains four tcrms. Plot each
i\lass.: Addison-Wesley, HISS, Chapters 36, 37, 38 energy levels discussed in the previous
of the terms as a function of A. For the
10. Princip/ea of Modern Phyatu, It. Leighton. New York: i\IcGraw-Hill, 1959, Chap- Ilroblem is also proportional to I . J, where
appropriale Z and N values for the fourth
~ tel"8 13, 14, 16, 18 aud 19
I i~ the nuclea r spin and J the electronic
term, lISC those correstlOnding to the most
angular momentum. Analyze the hyper-
II. Nm:lear Phyticr, I. Kaplan. Readi ng, Mass : Addison-Wesley, 1963 stable i$obllr nnd choose only selected 0'1
fine splitting of the elect ronic states 281/2,
vahles. Determine the relative imllOrttlnce
12. Introduction to tht 11 lomie N14c/t141, J . Cuninghame. Amsterdam: Elsevier Publishing ZPI /2, and 21'a/2 of 23Na (l - i). In each of each term in the different regions of the
Co., 1964 CIlSC determine the number of leveill and
periodic table.
their relative spacing. Show you r result~
7.17 With the aid of Eq. (7.13), determine
on an energy lenl diagram.
the atomic number of the stable nuclide for
7.11 The eledric qU9.drupole moment of tI _ 27, 61, 82, 125, and 180. Compare
an ellipsoidal charge distribution which these va lues with the dM:!. in Fig. i -I.
has allinl symmetry is Q _ ",Z (a2 _ /)2),
7.1 8 r "ing the Weisz.iicker formula, csl-
where a is measured along the symmetry cul:J.le the atomic maSileS of 12C. 21AI, S8S r,
7.1 Ellamine Fig. 7- 1 (o r Ihe thart of 7.5 Calculate the nuclear radius of 100, axit and /) is measured along the perpcndie-
!205n , and 2osPb. I S~ne, aud 232U. COml)are with the values
nuclides provided with the text) carefully ulnr direetion. The mean nuclear radius R
to verify the IItatement that adjacent IItable listed in Table 7- \ and judge the accuracy
7.6 Choosing the most abundant isotope, is defined by R2 _ 00 2 . (This guarantees
isobaric l)flirs do not occur in nature. of the formula.
compute the nuclear radius for nuclidCli that a "phere of radiU!! R has the ~ame
7.2 Make a list of all adjacent stable iso- 7.19 Using the Wcisllicker formula, cal-
with Z equal to 10, 30, SO, 70, and 00. \'olume iii! the ellipsoid.) Show t hat if
topic !!eta larger than 4. For example, Also compute the radius of the inner elec- a _ R + ilR, then /) - R - ;ilR and culAte t he mass difference between the
mirror nuclci 23Xa Ilml 23)lg. Compare
tilanium (Z - 22) has five adjacent sta ble tronic orbit, ming Eq. (3.11). Plot both Q - ~Z R toR , to the first order of Illll)roxi-
wilh the result u~ing the experimental
isotope5. VIIC Fig. 7- \ or the chart of nu- radii on the same graph. Draw conclusions mation. l\il;o note that Q/ ZR2 , which is
clides provided with the text. vslues of the mllSSC!!, which are 22.989/7
about the interaction of inner electrons plotted in Fig. i-4, is proporlion!ll to
and 22.99112 aml1, rcsIICCth-ely.
7.3 Wilh the aid of Fig. 7- 1 (o r the chart with the nucleus. toH/ H. Determi ne whether this Illot is
morc informative than a plot 01 the qua- 7.20 (a) Cftlculllle the binding energies
of nuc lidCll), invClltigate stablc i40tonic 7.7 What nuclei have a radiua equal to
drupole moment alone, fI.S far as information for HO, I~O, 160, !10, 180, and I~O.
sets. Writc the neutron number N for sets one-half the radius of 23SU?
nbout nuclenr deformation goes. (b) Repent for l~ C, 1~~, 160, 17F, and
of more t han fouf stable isotoncs. Are any 7.8 Estimate the kinetic energy of a nu_ !8~e. (e) From the results of (a) and (b) ,
of these adjacent stable i!!Otones? cleon inside a nucleus, both by using the 7.12 Using the data of Table 7-1 and the c~p\(lin the variation in binding energy
7.4 Ordinary boro n is !~ mixture of the quantum-mechanical picture of a particle rC!\uhs of Problem i .JI, estim!lle il III Il 1l.S II. neu tron or a proton is added to !lo
l0B and 11 B isotopes. T he compositc (or ill a potential box of width 10- 16 maud for J7dl.u, which is one of the most highly nucleus. The masses of those nuclei not
chcmical) atomic mass is 10.811 amu. by considering the de Broglie wavelength}, deformed nu clei. listed in Table 7- 1 :ire (in amu): He,
What percentage of each isotope is present of the nucleon, which is of the order of 2,-r, 14.00324; 140, 14.00860 ; I~O, 15.00307;
7.13 Esti mate the coulomb repubion
in natural boron (a) by number and (b) by where T is 10- 16 m. encrgy of the two protons in 31le (nssume L80, 1;.999t6; 11l0, 19.00358; 17 F, 17.00209;
mass? !8~e, 18.00.s7J.
that they are 1.7 X JO-u m apart).

326 Nuclear IIrudure
7.21 The follo"ing mll.SS diifell"nces have
been found experimentally:
1112 _ 211 _ I.M34 X 1O-3 a mu ,
3 211 _ ; 12(' _ 4.2300 X IO - ~alllu,
12C III~ _ leO _ 3.6364 X 1O-2 anlu .
On t he bs ... i;s of I~C - J2.000:unu, caleu-
Iste t he atomic ma..~s of I II , 211, lind I$Q.
Comll!'Lre with the eX]K'rimentl.1 value!.
7.22 A simple enlpiricalap]lroximation for
the nuclear poteutial i~ the Yuka\\"a poten-
tial E. _ - Jo.'or-<Io/r, wher('
Eo - 50 " leV lind '0 - 1.5 X 10- 1:' m.
Plot the Yukll. wa potenti:L.1 for r - O.l ro,
0.5ro, ro, J .5ro, 2ro, fi nd 3ro, lind compare
with the electri c potential ellerg), of t"'o
protons at th e ~/Une scpllrntions.
7.23 Show how the 3S, II', 31', lind 3D
states of !\ neutron-proton system are the
only ones eompntible with a nuclear spin
equnlto one.
7.24 It Clln be show n that, when all1lhase
shifts lire considered, the 8Cnttering am pli-
tude f (8) of neut ron 8CaUering ia given by
f (6) - i E, Y/4w(21 + I) iLei'/sin oS,l"IQ,
where 8 is th e &tattering angll' and the r IQ
arc angular momentum funetiolls. When
the energies are not too great, only thl'
first two phase shifts, oSo and oSl, are needed
to d~ ribc the Ileutroll &tattering and all
other phase shif ts are Il'ro. (a) Write f 1.8)
and the differenlinl erOM ~ection u(8) for
t his app roximation. (b) Sho"- that the
scattering ig not spheri callY symmetric.
How do you correlate the asymmetry wi th
the signs of t he phase !l.hift~? (e) Compute
th e totnl cross section by integrll.lion a.nd
verify that it coincides with the fir~t two
terms ill ::q. (7.22). [lfint: Use the expres-
sions for 1'00 nnd ri O given in Tnblc 3-1.)
7.25 Show that, in lUI elastic !!Cattering
experiment involving protons on protons
or neutrons on protons, no particles sre
scattered more tlmn OOG in the labora.tory
frame of referellce. (.\ SI<lllne equal masses.)
[llint: ese the nonrei:ltivil;tie formul a.,
relating the scattering sngle in the C- IIlId
I.Arsmcs of reference giv('n in the apll<':ndix.]
i.26 Through what angle in the Isboratory
frame of reference is a 4-;\leV (I-particle
scattered when it apprOll.ehes 11. gold nu-
cleus with Jut impact parameter which is
2.6 X 1O- 13 m r
i .Z7 What is the imlmct 113rameter of a
4-;\ [eV a-particle, given tha t it is lleattered
cleon-nucleon !!CatteriDg in the triplet
through an allgle of 15 by s gold nucleus?
i .28 Find the distance of cloSl'St 111)-
]lroach for (a) 100!\l eV and (b) SO-MeV
protons, incident he!l.d-on on a gold nu-
cleus, and compare with the nUC\('llf radius.
(c) In which case will the proton "hit" the
nucleus ? Find the kinetic energy of th e
proton when it "hits" the nu cleus.
i .29 ,\11 aluminum foil S('atters 103 (1-
pll.rticles per second in a given direction .
If the [lluminum foil is re]llaced by a gold
foil of identical thickness, how mallY or-
particles will be scattered per second in the
same direct ion ?
i.30 The number of or-Ilart icles 8Cattered
by a given foil is lOGper second at a scat-
tering sngle of 10. Calculate t he nu mber
of or-particles 8Cattered at each 10 interval
up to lSO. Plot your relIul lJl for a(8).
i.31 A beam of 12.i5-:\leV or-partie1es is
scattered br an aluminum foil. It is found
thaL the number of particles scattered in a
given dirtion begins to dc,-iate from the
predicted coulomb scattering "alue at all-
proximately 54. If the or-particles are
lllSSumed to have a rlldius of 2 X JO-u m,
estimate thc radius of the aluminum Ll U-
c1eus. [I/int: It can be shown that th e dis-
tance of closest approach is given by
7.32 At wha t neutron cnergy does th e
re1:\lio n k X r:l.n ge of nuclenr force - 0.5
hold? Could this result be used to estimate
the upper limit of the enl'rgy a t which only
lHlCattering of neutrons by protons need be
considered ?
7.33 Calculate the nucleon-nucleon scat.-
tering cross lIeCtion in lhe limit of low
energiea, E ..... 0, for the triplet potential
(Eo - 36.2 MeV) and the singlet poten-
tial (Eo - 17.8l\leV). What cross seclion
would be measured experimentally if the
~pins of the particles ,..ere to be oriented
rtlndomly?
7.34 Calculate the cross section for nu-
state ( 5 0 - 36.2l\IeV) for E - 0.1,0.5,1,
and 5 MeV. Do you conclude then that at
lo w cnergies the eross section for nucleon-
nucleon scattering is not scnsitive to the
energy ?
7.35 (a) Using the shell-model scheme
given in Fig. 7- 16, find the nucleon con-
figuration for ~H, 3R, 3He, tHe, 7Li, nC,
IlIC, and uCI. (b) Predict t he nuclear spin
for these nuclides. Compare with t he values
listed in Table 7- 1.
7.36 Compute the magnet dipo le momen ts
of the nuclei lil;ted in the previous problem,
U3ing the method of Example 7.6, and
compare ,..ith tbe experimental values
given in Table 7-1.
7.37 The momeDt of inertia of a nueleu~
of Il\a5lI M and average radius R, if COD-
sidered a solid sllhere, is !l - fM R~.
With a mll88 number _4 equal to 50, 100,
and 150, estimate the energy (in MeV) of
a l'-ray emitted in a t ransition from a
rotational energy level ""ilh I _ 2 to one
with I - O. Comp~re ,..ith the energy of
"""(-raYli emitted by even-even nuclei in those
regions. What do you conclude?
7.38 From the rotational energy levels
shown in Fig. 7- 20, estimate the moment
of inertia of IsoII{. The moment of inertia
about the symmetry axis of an cllip'lIoid of
re volution is !l - f Mb~, where b is the
length of the other IICmiaxCII. Estimate the
deformation llR/lt of 180Hf, and compare
",ith the value obtained from the electric
qu adru pole moment. [fl int: Recall from
Problcm7.llthat b _ R - ! llR.J
7.39 Referring to Fig. 7-22, determine the
cnergy and multipole order of the l'-t ransi-
tiona shown for each of the three nuclei.
7.40 Rcfer to Fig. 7- 22(,,) and (b), and
assume that each of the levels shown is due
to a single particle transition; with the aid
of the shelJ-modcllevel !!Cherne of Fig. 7-16,
write the configuration for lhe ground state
and caeh of the excited states.
7.'11 ne.ferring to Fig. 7- 22(c) , deter-
mine whether or not the level scheme can
be "ttributed 10 rotational colItive
excitations.

8.2) Radioocli~ duo.y 329
8 11. 1 InlrOflm:tlm'
NUCLEAR PROCESSES I n the previous chapter we analyzed the basic properties of nuclei, considered as
stable assemblies of Iluc!oons, and pro]>oscd a model which, in :\ more or less sat-
isfaciol"), way, accounts for such ]>ropertics. Another source of information about
Iluclenr slnlcturc is the analysis of processes, such as nuclear disintcgmlions and
nuclear reactions, in which there is a rcarrallgCl\lcnt in the energy or oonfiguratioll
of the nucleons. In this chapter we Shl.1! analyzo some nuclciIr processes. l\[nnyof
them occur 1l:lturally, but others are I)roduccd nrtificially in ihc laboratory using
different types of nccelerating machincs or nuclear rC3ctors. The experimental and
theoretical discu.':'Sion of nuclear processes is still an unfinished chapter of eOIl-
temporary physiC'l, in which a large amount of research is being dOlle.

11.2 Ittlfllmlf: tl,',' lIec tlll

We remind the student thal, when we were diseussing Fig. 7- 1, lI"e indicated that
some nuclei h3ve II combination of l)rotons and neutrons which docs not lend to a
stnblc configunltion. T hese nuclei are therefore unstable or radio~tctive. Unstable
nuclei tend 10 approach a stablc configuration by releasing certain I)arlicles. These
]>articles, when they were firs t observed Ilt the end of the last century by J. Bee-
qucrel, Pierre !lIld jo.bzie Curie, and others, were designated as a- and ,B-pnrticles.
Alpha pnrticles arc helium nuclei, composed of two protons and two neutrons
3JI may be verified by me3JIunng their charge and IllflSS. Thus when ll. nucl~us
emits an :Ilpha particle its atomic number Z decreases by two units and its maS'!
number A decreases by four units. The new nucleus therefore corresponds to a
difTerent chcmical element. For exarnple, when the rndioactive nucleus 7:fU emits
an a-p~lrticle, the residu:tl nucleus is 7:~Th.
Beta p3rtieles arc electrons which cnrry a clmrge - to Hence, when a nucleus
8. 1 I ntroduction emits a p-p..'lrticle, the atomic number of the nucleus increases by one unit, but the
8.2 Radioactive Decay ma.ss number does not changc. For example, when the radioactive nucleus 2~~ Th
emits a .B-pnrtielc, the residunlnucleu8 is tgt Pn. SOllie nuclei, instead of emitting
8.3 Alpha Decay electrons, release positrons which carry tl. charge + tj therefore the residual nucleus,
8.4 Bela Decay after positron emi:;sion, has an atomic number smaller by one unit. For example,
8.5 N uclear Reactions when thc nucleus !1N emi!s n positron, the residufd nucleus is ! ~C. The two types
of ,6-<iecny nre designat ed ,6- and p+, rcspecli\cly. T hc residunl or duughler
8.6 Nuclear Fission nucleus is sometimes lefL in 1m excited Slate i\nd in the tran.sition to its ground
8.7 N uclear Fusion atate emi ts g:l1l1nltII"IIYS, as explained ill Scction 7.10.
!\Iany isotopes of clements lI"ith Z > SI (or II > 2OG) are naturally radioactive.
8.8 The Origin oj the ElemenLs A fell" other naturally existing lighter nuclci, such as HC and ~o l \, arc nlsa radio-
active. ?dany more mdioncti\'e nuclei havc been prodllced in the I:lboratory using
nuclcnr reactors and particle :Iccclerator",. Figure 8- J shows onc of the .. hree natural
radioactive ('hains, the SO-C~lllcd uraniUIII serit8, and T lIble 8-l gives the relcvant
informatiOIl about this serics. The mll5S number of nuclei in thi'" series is givcn by
4/! + 2, where 11 is lin integcr. The \ wo other IInturaJ mdioactive chi\ins are the
actilll'UIII 8(ries i\nd the thQrium series, coml)()S('(1 re,,]>cctivcly of lIuclei of type
 po

330 NlUkar prOCtlltl (8.2 8.2) Iladiooclife deroy 331

, T ABLE 8-1 T h e Ura l1iu m Series

, kt'
U~~X_~ U I [
uz......., Radioactive species Nuclide
Type of
diJJ.inte- Ball-life
Disintegration Particle
energy,
constsnt, B- '
, gration MeV
,

H
.. Th
Uranium I (UI)
Uranium X, (UX, )
Ursnium X? (UX?)
n~U
t3~Th
1:~l'a

P
p
4.51 X 100 y
24.1 d
1.18 m
4.SS
3.33
9.77
X
X
X
10
10-'
10 - 3
" 4.19
0.19
2.31
, ~ I{n
Uranium Z (UZ) 2~~Pa p 6.6611 2.SS X 10- 5 0.3

I
UraniU'1l II {UII ) I~~U
2.4S X 106 y 8.80 X IO- H 4.i68
:;;Z n.,\-f,\t
ThoriUJI\ (Th) '::Th
2~;Ra
8.0 X 10~ Y 2.i5 X 10- 13 4.68

" Radium (Ra) 1620y 1.36 X 10 - 11 4.i77

2 11 It& I~ Has:tHaC'
Radon (Rn)
Radium A (RaA)
T,iiHn
2~:PO

.,p
3.82 d
3.05 m
2.10
3.i8
X
X
IO- G
10- 3
5.486
a:5.998

2 10 HII('~2 Hl\~~lb~'
I Radium 13 (Rab) 1~~I'l>
2~At
p 26.8 m 4.31 X IO-~
{J:
O.i
?

Il"G
Astntinc-2lS (2[8At)
Radium C (RaC) 2;Jfli

.,p
1.3 S
19.7 m
0.4
5.S6 X 10-1
6.70
200 a:5.51

10 Pi> III ,,, ,\\ .Em h H ."89 '1'1> P. r Radium C' (RaC') 21:1'0 1.64 X 10- s 4.23 X 103
{J:3.1 7
7.683
" 82 " " 8b .s6 87
.\Iomic number
88 00
" Hadium C" (R."1.C")
Badium 0 (RaO)
2!?Tl
3:gl'b
P
p
1.32 III
21y
8.75 X
1.13X
10 - ~
IO - ~
1.96
0.01S5
Fig. 8-1. The mtturally rad ioac ti ve uran ium or 4n + 2 series. Ih.dium E (lbE) 2~Ui P 5.0 d 1.60 X IO- G 1.155
Radium F' (Ralo') 3l~Po 13So4 d 5.80 X 10- 8 5.300
4n + 3 and 411. T he heavier nuclides in these two series are 2:tU and 2:~Th. It ThaLlium-206 (206T1) 2OJ':Tl p 4.2m 2..75 X 10- 3 1.51
Hadium G (RaG ) ~Pb Stable
is suggested that the student make a plot of these two series, similar to Fig. 8-1,
using the chart of nuclides provided with the text.
In the next two sections we shall
present a more detailed Illlalysis of a- and
,B-decay. But let WI now discuss certain .\'0 tillle illterval T, called the half-lIfe, durillg II hich lhe /lumber of nuclei at the be-
fentures that nre common to both radio- ginning of the interval is reduced, by the end of the interval , lO one-half. So if
active processes. It has been observed we inilially had No nuclei (or ;Homs), after tillle T only N o/ 2 nrc left, after time
that all radioactive processes follow an 2T only NoN remain, and so on. To find this time T, we set N = !No and t = T
exponential ]!!.\\,. T herefore, if No is the in Eq. (8. 1). T hen ;No = Noe - ~r or e~r = 2. Taking logarithms, we have
~T = 11\2 = 0 .693 or
in itial numbe r of unstable nuclei, the N0/2
number of nuclei remaining after a time
T = 0.693/ }., (8.2)
l is given by
N = Noe-~I, (8. 1) "'014
which relates T and~ . T he recorded hillf-lives go from a great mllny years- such
where ~ is a constant characteristic of N0/8 the half-life of the a -dctay of 2oo13i, which is about 2 X 10 18 years, and the
II.!!
"'01 16 N0I32 P--decay of [ 15 rn, which is about 0 X 10 14 years- down to fractions of a second
each nuclide, called t.he disilltegratioll
constOllt. It is expressed in S-I (or in the 0 l' 21' 31' .r 3,. (gl3e has au a-dccay haJf-life of the order of 10- [6 s).
reciprocal of any other lime unit). Equa- From Eq. (8. 1) we M il find the rate at which Iluclci disintegrate:
t ion (8. 1) is reprCIICnted in Fig. 8- 2. For F ig. 8-2. Radiooctive decay lUI a function
each radioaclive nuclide there is a fixed of time. (8.3)
 ..
(8.2 8.2) nadioacli~ duay JJJ
JJ2
EX.AMPLE 8.2 . .O~e methoo of prod ucing a radioactive nuclide is to place 0. sa.mple of
This indicnlcs that the disintegration rate dN j dt is proportional to the number of
a gIVen lI ubi;ta.nce Ins.de a nuclear ree.clor. Radioactive nuclides o.re produced as lI. result
nuclei present. Therefore the disintegration rate dN f dt decresscs in the same ~! neut.ron capture by the nuclei of the substancc. )o'or example, whcn we bombard
proportion and with the same half-life as the number of nuclei N. The absolute Co With neutrons, ,,'e find that ...e obl.ain toCo, which is ,8-radioactive with 0. half- life of
value of thc disintegration rale, JdN j dt], is called thc activity of the substance. 5.27 yea:-,. Another m~thod of oblo.ining radioactive nuelides is to bombard thc sub-
Disintegration ratC8 arc usually expressed in curielf, abbreviated ei, in honor of Btance ~It~ charged parlleles, ~ uc h as protons or deuterons, using sceeleratol"ll to energize
P ierre and 1\lar;c Curie, discoverers of polonium and radium. The curie is defined the l)roJectilcs. In both cases the ne ... nuclide is produced at the tollllt&nt rate of g nuclci
as the activity of a substance ill which 3.700 X 10 10 nuclei disintegrate per second. per .second. Calculate the number of nacki of the radioactive nuclide produced in terms
SubmultiplCfl of the bnsic ullit arc the millicurie (I mCi = 10- 3 Gi) and the micro- of time.
curie (1 ,IoCCi = 10-' Ci).
Equations (8. 1) llnd (8.3) lire both statistical laws which are valid only when
'00 -- - - - - - - - ------------ - ---:..\~,-.. ~j).
the number of nuclei is very hu'ge, and which may be interpreted in Lhe following
way. There is a decay /ITOOabilily peT unit lime X that an unstable nucleus will 0.7$
disintegrate according to a specific process. T he prohabilit,y that the nucleus will
disintegrate in the Lime interval dt is X dl. If there are N nuclei present (where N 0.50
is very large), then we may ex pect a. number of nuclei equal to (X dt)N to disinte- O.Z.'i
grate during dl. T herefore we may write
U '-----C,~'-----~";r-----'~,O'-----'O,c'----c'l.T,--
dN = - (X dt)N 0< dN/dt = - XN ,
fig. 8-3. Production of a mdioo.ctil'c nuclide as a function of time.

which is E q. (8.3). T he minus sign nppeal'S because N decreMcs with time ItS a
result of the dCC:1Y. The calculation of the decay probability per unit time X for
each dcctlY process is an importa nt problem for which refined tcchniques of quan- 501,,tio,,, Th~ rsdioactiv~ nuclide ill fabr icated at the rate of V nuclei per setond, but
tum mechanics must be used. Note from the above discussion that we cannot o.t th~ Bame time, accordmg to Eq. (8.3), the nuclide di8integrates at the rste of XN
speak of the half-life of a single nucleus or predict with certainty when a given nude. ~r second, where N is the number of nucle i present at that instant. Thus the net
rate of llIcrease of nuclei per second is
nucleus will disi ntegrate, and we repeat that Eqs. (8. 1) and (8.3) are correct only
in a statistical sense. dN
di ~ g-XN .
EXAMPLE 8. 1. Compute t he m!lSil of 1.00 Ci of '''C. The half-life of liC ilI55iO years.
Sepamting the vo.riablcs o.nd integrating, ...e have
5011,';01" Since T _ 5570 yr ... (S.5iO X 103 yr) X (2.I56 X 107 s/ yr) ... 1.758 X 10' I S,
12
the disintegration tonstsnt is X .. 0.693I T ... 3.94 X 10- S-I. '\00
log N -g(>.. __ }.j
IdN l dtl .. I Ci .. 3.iO X 10 7 6-' . No g(>.. .

Therefore, using Eq. (S.3) with o.bsolule \'alues, we find that Aasumi ng that the number of nuclei of th e substance was initially zero (that is N = 0),
we have, at a later t ime I, ' 0

N .. >:1 \dN\
Tt .. 9.38 X 101nuclei
8 of 14 C,

which is lI.lso thc numbe r of car bon ato ms present. The atomic mass of HC is 14.0077 amu.
Thus t he mll.S3 of the nbave numbcr of curban atoms is
.\1 _ ( 14.0077 X 1.6604 X 10- 27 kg atom-I) X (9.38 X )018 a tOIll.'!)
_ 2.18 X 10- 7 kg.
This T:lle is app roximately eq(LlI. I to the lI.cti\'ity of I g of UII.
:rhe mo.ximum number of radioactive nuclei tlmt call be produced und er these co nditions
16 N m .., .. V/}: . The variation of N with (is illustrated ill Fig. 8-3. Note t hat at time
( .. T, we have O.50g/). atoms and at I ... 2T we have 0.75g(>.. atoms .
The student should recognize th at this equo.tion is mathemll.tically identical to that for
~ree fall of a body in a viscous fluid or for the growth of an electric current t hrough""
.nductance .
 ...
334 Nue/tar pr0Ct!3UI (8.2 8.3) Alpha decay 335

"; ,'I(AMI' I.E B.3. Substance.l di~inlegrates iuto another substance H, which is also the number of nudei of C is equal to N AO. The variation of II' A, N B, and Ne with time
radio:l.I':tivc. Gi\'cn th:t.t AA. and X" are the respeeth'c disintegration constants of A and B, is illWltrat.ed in Fig. 8-4. At lhe beginning we note thnt B increa.ses because it is pro-
find lhe \':uiation Qf B as a hlnelion Qf time. ANulne that the initial amount Qf B is aero. duced faster than it disintegrates. But, after Il ceruin time, the situation TeVCI'lICS be-
cause the activity of the parent substance has dooreased. The rcsulls can be extended to
Sul"rioll: Actorrling tn Eq. (8.3) , substance /\ disintegrates at the rate more complicated radioactive chains tI --+ 8 --+ C ..... D --+ ,such as the natural radio-
active seri es. A study of these chains is useful, for example, when we wish to determine the
age of rock3 containing radioactive substances by finding lhe proportion of each sub-
stance in a sample of the rock.
so that N.I _ N ,lOr l A.'. For each nudem nf :I that disintegrates, onc of B is formed.
Thus B is formed at the rale nf }"AN A nuclei per !leoond. At the 83.me time, however, it
disintegrates at the rate of }o./tN II nuclei per second. Therefore the net increase of nuclei
of B per unit time is
As we saw in the previous section, alplm decay consists in the emission of an a-
dN ll -
"(j!" ' "
"AI>.toe -~A' - ' "
I\B I B.
particle (or helium nucleus ~ I:l e), composed of two protons llnd two neutrol18. The
daughter nucleus has an atomic number two units less and a mass number four
units less than the parent. Thus, if we denote the parent and daughter nuclei by
The solution of Ihis equation which .'I8tillfitll the condition that N B ... 0 at time t ... 0,
~ the student may verify by direct substitutioll, i~
X and Y , respectively, we may write the process of a-dccay as

~x -+ ~=;y + ;He. (8.4)

}<'or example, ':iu is an a-emitter and disintegrates according to the scheme

If substance B disintcgrJl.tes into a stable ~ubslAnce C, then the number of nuclei of C
increase!! stcadily until, after :l. \'ery long time comparoo with the half-li\'es of tI and B,

Most a-(!mitters are heavy nuclei, corresponding to nuclides at the end of the peri-
odic table. In fact, it can be shown from the expression fo r the nuclear binding
N", energy, as given by Eq. (7.10), that most nuclei with A > 150 should be a-(!mitter:;.
However, the majority of a-emittcr nuclci have A > 200. It. is supposed thal,
\\'ith a few exceptions, the half-lives of lighter nuclei for a-decay are so long that
this decay mode is practienlly unobservable.
file
\ An a-pnrticle is a doubly magic nucleus consisting of two protons and two neu-
trons, all in an s1l2 shell, having a zero total spin and even parity. T hus a-I)articlcs
have an extraordinary stability, and therefore behave in many instances as a single
unit or particle, similar to protons and neutrons. The student may recall that
Rutherford used a -particles as projectiles to probe the interior of the atom and
establish the nuclear model.
We must Ilot think, however, that a-particles exist 115 such inside the nucleus.
Supposedly there arc certain correlations in the motion of the nucleons which
occasionally cause some of them to group themselves into an a-particle-like con-
figuration which, for a short time, acLs as a dynamical unit. When Buch a unit is
near the surface of the nucleus, there is a certain probability that the group of
nucleons escapes as an a-particle.
The potential energy of interaction of an all)ha particle with the rest of the nu-
cleus, which is very similar 10 that of a proton with the rest of the nucleus (recall
Fig. 7- 1), is indicated in Fig. 8-5. The energy of the a-particles (about 4 to!) MeV)
Fig. 8-4. Rndioactive !jCrie! with three members. Only the parent, A (T ... 1 hr) is is less than the height of the coulomb barricr (about 40 l\ leV for most a-cmiUers)
initially present. The daughter, 8 , has a half-life of 5 hr and the third member, C, is stable. at the surface of the nucleus, and the a-particle can escape only by penetrating the

JJ6 (8.3 8.3) A/phil dffllY JJ7

, nuclei by collecting (in an evacuated tube) the a-particles ejected from n substance;
when tin electric discharge was passed through the tube, the spectrum of hclium
Potential Imrrier
was observed.
T he range of a-particles depends on both their cnergy and the substance through
which they move. Their range in ai r at STP i8 only a few centimetcrs. For ex~
ample, a-particles from 210pO (5.3 :\ lcV) and from 2HpO (7.7 MeV) have ranges
in air of about 3.8 cm and 7.0 cm, respectivcly. However, a-particles are easily
absorbed by a sheet of paper or a very thin aluminum foil. In Fig. 8-6 we observe
that the a-I>articles producing the tracks fall into two gro\IPS, eaeh with n charac-
teristic range.
T he fact that the a-particles emitted by a given nuclide have a well-dcfined
range is nn indication that thcy also have a wcll-defined energy. Figure 8-7 shows
Nuclear the energy spectrum of the a-particles emitted by i\ numbe r of diffcrent nuclides.
au,nld.ion
T he energy, in arbitrary units, oorresponds to the channel numbers of an energy-
Fig_ 8-5. Potential energy of an u-particle analyzing device. One cnn clearly see that the cr-I>articles from each nuclide have
lind a nucleus. a well-defined energy. This fllct oonfirms that a-decay is a two-body problem, as
expressed by Eq. (8.4); thus a-decay resembles the explosion of a grenade into two
fragmcnts. We assume thtlt, in the process of a-decay, cnergy and momentum are
Fig. 8-6. Tracks of a-particles in a cloud conserved. If Q is the energy released in the decay of the parent nucleus X, as-
chamber. The deviated track appears to be sumed at rest in the labomtory, the kinetic energies of the a-parlicle and the
due to the reaction uN (II', p) 170 which bas taken place with a hydrogen atom in the daughter nucleus Y after they nrc fnr apart [see Appendix J r, Eq. (A.27 )] are
chamber. Two groups of a-partie1es, each wilh a characteristic range, are dearly recog-
nizable in this photograph.
Eta = my Q
m,, +my ,
ElY = ':;.... Q. (8.5)
m" my
potenti!.l barrier (Scetion 2.8). We can coml)lltc the disintegration probability
per unit time, A, in terms of the probability P of penetrating the barrier. The quan- ,HdTh. [,,42 ~]eV
>000
tity P is computed using the methods of quantum mechanics. The results agree TIlX,
fairly well with the experimental values fo r A. ',68
:'leV
From Fig. 8-5 we see that the higher the kinetic energy E... of lhe a-particle
,
1iSOO
the smaller the height and width of the barrier, and therefore the larger the protr
ability P of penetrating the barrier. Thus we may expect that the disintegration
l!
o
700 ,,"
T,.
~]eV
Th.\ ,
6.77
constant" will increase with E b , a fact we cnn verify by inspecting Table 8-1. 11~1O The,
~leV

A detn.iled cn.lculation shows that the transmission probability P is vc ry scnsitive .= ;,00 6.05
to the height and width of the barrier, and thus to E k ". T his explains why (as ~~
seen in Table 8-1) a change of Eb by a facto r of about two from 4.20 l\ leV
(which corresponds to uSU), to 7.68 :\leV (which corresponds t-o 214 p O), resulla ~:
) Th(".
S.i~

in a ehnnge of A from 4.88 X 10- 18 8- 1 to 4.23 X 10 3 5-1, or n fsctor of about 10 21 . ~ 2110 :\]eV
Since a-particles nre charged, they ionize the atoms of the substnnce through
which they propagate. This constitutes one of the methods by which a-particles .'" \"J V \
can be detected, using devices which either mell.8urc the amount of ionization (such
0
7!U I;>- .!If ,-
2., 3(1 --
3., 1(1 -
j., -
.,(1 --
.>., 1\0 r",- 70
-
7., I'll
ll.8 ionization chambers) or make the ionization visible (as in cloud chambers). {I."""cI ."""h"r (C"NIO')
Figure 8-6 shows a eloud-chamber photogmph of a-particle tracks made by 11 radio-
Fig. 8-7. Thc a-particlc cncqcy spectrum from 1\ sample of radio-thoriunl (22STh) and
active sample. As a result of the ioni~ation, the a-particles lose energy until they it:<! dcscendants. Wrom the National A'1U:l~ar t:'N!rgll &rua, Vol. 14A, Th~ Aetinith
slow down sufficiently to pick up two electrons nnd become neutral helium atoms. EI~menl', G. Seaborg and J. Klltl, editors. Ncll' York.: :'>leGrs"'-Hill, HIM, Chapter 16.
It WM Rutherford who (in 1919) first demonstrated that a-par~cles arc helium With the permission of the United States Atomic Energy Commission.]
 pi

338 (8.3
8.3) Alpha dtwy 339
Encr~,)' ~I)(),c KroImtl
~t~le III The", :'>lcV The value of Q is obtained from the mass change in the process; that is,
The (~ 1 2Bi )
6."" -- - - - - - - - - - - --- - - -,--ii7-'T-,- Q = (mx - my - m~)c2, (8.6)

since mxc 2 is the intl!rn nl energy of the parent nucleus and myc 2 and m",2 are the
internal energies of the two products [see Appendix 11 , Eq. (A.22)J. Of course, for
a- particle emission to occur, i~ is necessary that Q > O. If t.he masses are ex-
pressed in nmu and Q is expressed in lHeV, then E q. (8.6) becomes
Q = 931 .48(mx - my - m,,). (8.7)
0.619
.., (o . IH ): In this equation t he masses may oorrespond either to the nuclei or to the ntoms,
0.492 since t he elcctron masses canccl when atomic masses a re used.
0.473
Y (OA32)

l' (O. 14" )

, .,. (O.lG ~ ) Strictly speaking, the o:- part icl~ frorn a given nuclide do not all have the same
energy; rather t hey exhibit a certain fine structure. For example, the o:-particles
0.'" from 238U have energies of 4. 18 i\lcV and 4. 13l\ IeV. The reasoll fo r this is
.,. (O.a2S) ., (OA;);!) that, although the parent nucleus Illay be in it.'! ground state, the daugh ter nucleus
l' (U.2N'l) .., \O.(72)
may be formed in its ground state or in all excited stationary stntc. T his situation
is illustra ted in Fig. 8- 8, which shows the dccay scheme of 2128 i (or 'fhC); t he
six o:-particle t ransitions (as well as the subsequent 'Y-mys emitted) are indicated
0.<0 =:r'-t-''-t--'----L
., ~'''''~"~
-
) '----',=,-J.=,-----'
n,( '" f'O"Tl)
by the arrows. In othcr cases, the reverse situation occurs. T he parent nucleus
may be in the ground stale or in one of seveml excited states, and the daughte r
nucleus be in the ground state, as shown in Fig. 8- 9 fo r t he disintegration scheme
Fig. 8-8. Disin wg rlllion scheme foro-<ieeay of 212m to 2011'1'1.
of 21~pO (or ThC'). Some 'Y-transitions arc nlsa shown.

Encrw;y above P'OUnd Ene"K)' nbovc lIn)Und EXAMPU-; 8.4. Compute the kinetic energy of o:-particles emitted from ~U.
nate of ThO, :\Ie\' Ie\'cl of The', :\[eV
11.20 - -- - - , r 2.19 Solutio", The decay process is 2~~U ..... 2~h +
~He. The masses which are in-
volved nm mx _ me 32 U) _ 232.1095 amu, mr _ m(22!1Th) _ 228.0998 amu, and

l~z~~S=$~ ",><
m. _ 4.0039 amu. Applying Eq. (8.7), we obtain Q - 5.40 MeV. A positive Q means
'6
that the process isexoergie and may occur spontaneously. By use of Eq. (8.5), we compute
t he kinetic energies as Eln. - 0.10 MeV and Eh - 5.30 rlleV. We obtain this value of
Et~ auuming that the 2ilo'Th is in its ground state. But if 23oo'Th is left in an excited state,
-r-+I+"'o-'1- 0 72 then the vslue of Eta is less. The experimental value of the most ellergctic o:-particles
from 23~U is Et _ 5.32 !\leV, so that our theoretical interpretation seems to be correct.

EXAMI'I. E B.S. Discuss the !ltability of ~U relative to the emission of other kinds of
partieies.
Solutio,, : We may wonder if, in addition to a-decay, some nueiei exhibit proton, neu-
tron, deuteron, or some other type of decay. No such decays have been observed because
the Q-valuC!! for these processes are negative. Therefore Lhese decays cannot oeeur unless
energy is supplied aod the parent nucleus is raised to an excited state, which may happen
in certain nuclear reactions. As an illustration, we msy compute the Q-values fo r the
emission of several kinds of llarticlC!! from the 232U nueieus, using Eq. (8.7) wilh ma and
mr replaced by the corresponding masses of the emitted Ilsnicle and the daughter nu-
ThO (81'1 deus. The results are lilltcd in Tsble 8-2. All Q'. are negative, !!O that 2UU ill stable
Fig. 8-9. Disintegration scheme for (r-decIlY of 21 ~Po to 208Pb. agsinst decay into such products. The reason a-emiilOlion by 232U is possible lies in the
relativdy small mass of the a-psrticle due to it.s relatively large binding energy.
 as

341) Nllc/u proUSIU (U 8.4) 341

TABLE 8-2 Q-Value8 (or [lI1i ll~ ion of Differe nt

Nuclear Pa rtieie, from 232 U 1.1 1 .\leV
r . 2. 77 .\ leV (3 1%)
(16'7~)
Particle i\lasa Daughter Mass Q, MeV
1.0000 UIU 231.1082 - 7.16 \'1 3.75
\i2.1(i
n
II(IU) 1.0081 231 P a 231.1078 - 6.05
de H) 2.0147 ~30 pa. 230.1060 - lOA
teH ) 3.0170 22~ Pa 229.1033 - 10.1
(.)
;S.\ 0
(d)
0.4 lIeta D ee11
III fo' jg. 7- 1 the stable nuclei were designated by black squares. In such a figure, IJ~, 1.11) MeV .1'>11 Io.o.~ r
those lIuclei lying above the stabi lity region emit electrons (charge -e), a process "0 fJ -, 1.67 .\leV (48%)
we have called (:J--decay. An eXI>erilllcnta[ result is that the daughter nucleus, ( 14%)
fJ. 1.84 .\leV
although it has the same nUlss number, has an atomic number larger by one than (>99"/0) a.oo
the parent nucleus. That is, it apl)Cars that in ,8--decay a neutron is replaced by
a proton, and parent and daughter nuclei are isobars. The process can thus be
expressed by
2.
30

o
3=:L
li:-;
IJ+, 4.1 )leV
(0. 6%)

~~~'
"
ffit
,
'Y 2.41
2.>2
2.08
(8.8) >'60
,
Note that the tota l charge is conserved, since the charge on the left of Eq. (8.8) <")
is Ze and on the right it is (Z +
I)e - e = Ze. Also the total number of nucleons --'_~
,,,,,,
~---'-.L 0
is conserved, s.ince A remains the same. For eXAmple, 14C is a ,,--emiuer and
(.)
transforms accordi ng to the sehcme

Similarly, in Fig. 7- 1, those nuclei lying below thc stabillt.y region suITer p+~decay, fJ-, 1.59 j\leV fJ -, 0.57 )lcV
EC (O.5~U
(30%) (39%)
a l>Tocess which consists in the emission of pwilrOll1! (charge +e). Positrons arc fJ '. , 0.66 .\lcV
particles with the same mass and 81>in BS electrons, but their charge is positive IJ~, (70"/0)
1.78 MeV ',\=~~0 1.015
'Y .7% (J9C'Ic) :
instead of negative. Positrons were predicted first on theoretical grounds by , , O.S3~ EC { ~ 42'7.;)
P. A. 1\ 1. Dirac in 1927 (as a result of some requirements of the theory of rela-
tivity which we canuOl mention hcre) and were observed for the first time in cosmic
rays by C. Anderson in 1932. It has been verified that, in ,,+
-deeay, the atomic
(c) II)
number of the daughter nucleus is smaller by one unit (again in agreement with
the law of collservatioll of charge) but that its mass number is the same as that of Fig. IHO. Disintegration schemes for \'ariOlllj ,8-emitters. (a) 2oF, (b) 140, (t) 27 M g,
the parent nucleus (in agrecment wilh the conservation of nucleons). Thus it (d) asCI, (e) H OLa, and (f) liCu.
appears that in p+-decay a I>roton is replaced by a neu tro n. Therefore the process
may be expressed by In some instances it has been observed that the parent nucleus, instead of emit,.
ting a positron, captures an electron from onc of the innermost atomic shcns, let
1x - z _~Y + e+. (8.') us say a K-electron. These arc 8-Cleetrons. Ai; the reader may recall from Sec-
As an exam ple, IIC is a fJ+ -emitter and transforms according to the seheme tion 3.5, &-electrons have very penetrating orbits which reach very close to the
nucleus; therefore their probability of being captured by a proton is relatively
l~C _ I~ B + e+. large. This process, called elul.ron capture (EC), also results in the replacement of

~ 1
342 Nu.clear processel
a proton by a neul ron in the daughter nucleus. I t can be expressed by
1x + e- ---> z_1v.
Once more note that the electric charge and the nucleon number arc conserved in
the process. Electron capture is followed by x-ray emission by the daughter
nucleus when all outer electron falls into the vacant state left in the }\-shcll. These
x-rays aTC the same as the characteristic rays of the daughter atom, discussed in
Section 4.7.
As in a-decay, the daughter nucleus resulting from ,B-dccay or EC may be left
in ils ground state or in an excited st.ate ; in the latter case the process is followed
by"Y-emission. Figure 8-10 shows the disintegration schemes of some beta emitters.
One of the more interesting features of .B-<iecay is that lhe electrons and positrons
arc emitted with a wide range of kinetic energies (and momenta), from zero to a
maximum compatible with the tot.'tl energy available. I n other words, the elec-
trons and positrons have a continuous energy spectrum. Figure S-11(a) shows
the energy distribution of the clectrons resulting from the fj--<leeay of 211Bi (or
RaE) and Fig. 8-ll(b) shows the energy disl,ribution of the positrons emitted in
the fj+-<leeay of IaN. Bul, Eqs. (8.S) and (8.9) arc two-body processes, similar to
",-<lecay, and the laws of conservation of energy and momentum require that in
the cenler-of-mnss frame of reference, in which the parent nucleus is a~ rest, the
energy available (the Q of the process) must be split in a fixed ratio among the
daughter nucleus and the electron or positron (recall Eq. 8.5 for a-<lecay). This is
in contradiction to the experimental result we have mentioned.
To settle this new difficulty, Pauli suggested in 1930 that another particle lllust
also be involved in fj-<lecay, so that three particles result. The third particle has
2118i
1.17 MeV
DO
o 0.' UA O.li 1.0 1,2 I) 0.25 O,t.O 0.75 1.00
Kinetic energy of de<:tron.~, :'I["V Kinelie energy of positrons, :'IIeV
iC'
Fig. 8-11 . (a) The energy spectrum of the electron emitt.cd in the fj-decay of ?HIli.
[Data from G. Neary, P~oc. Roy. Soc. (Lond?n) A175, 71(19~~)1 (b) The ener~y spectrum
of the positron emitted 111 the fj +-dccay of 3N. [Data by Slcgbahn and Slaus, Ark. As/.
Malh. fi'ytrt:k 32A. No.9 (19 45) )
>
(8.4
8.4) J4J
to be neutral, to comply with the law of conservation of ehurge, and of very small
(8.10) mass, since tho totallllass is essentially nccounted for by the other observed pnr-
ticles. l'or these two rcasons lhe nell' particle wa.s called 11 /leI/trilla. (This name
wa.s proposed by Enrico f ermi, and mellllS "the little neutron.") It. is designated
by the symbol Y. As we shall sec in Section !Ui, it h:1.$ ~n found that. there are
two kinds of neutral particles, almost identical, assoeinted with fj-deeay . One,
the neutrino, is emitted in 6 +-decay and electron cal)ture, while the particle
emi tted in .s--decay is called the Q/ltilleutril/O, lind is designatcd by v. However,
in this chllpter we shllilrefer in most cases to both particles by the name "neutrino."
Fig. 8-12. il l omcntulll con~rvation in .8-dccay.
The neutrino is assumed to cllrry away the energy :Irld mOlllent.um required to
restore the conscf\'ation of both qWUltities. In the center-or-mass frnme of refer-
eneo the momenta of the three resulting pllrticlcs must add to llero ( Fig. 8- 12).
But there is an infini1C number of ways in which the total energy available can be
split among lhe three products, and this very nicely explliins the continuous energy
distribution of the electrons or positrons. Therefore processes (S.8), (S.O), and
(8.10) must be rewritten in the following form:
(:1--<lecay: 1x ---+ z+1Y + e- + V, (S.11 )
fj+-<lecay: 1x ---+ z_1 Y + e+ + v, (S.12)
EC: 1x + e- ---+ z_~Y + v. (8.13)
13" So far we may say that the neutrino is an interesting invention to save two con-
servation lall"S. But. is there additional confirmation of its existence? On the theo-
retical side, one can make a statistical :lnalysis to determinc how the energy re-
leased in the dee3y process is sh,lred by the electron (or the positron) and the
1.24 MeV neutrino (sec Ex:tmple 8.8). When this analysis is compared with lhe experimental
energy distribution of the electrons (or the I>ositrons) and the neutrino, excellent
agreement is obt:lined, provided 1hat the rest mass of the neutrino is very small
(tess than 1O- 3 m.). Actually the neutrino's rest. m:l&l is considered to be zero
1.25
(m. = 0), :lnd thus for i~ neutrino the energy-momentum relation is E. = cp.
On the expcritncntnl side, i[' is easy to understand that, because of its properties,
the neutrino should be very difficult to observe, since it is insel!lSiblc to the action
of electric iltld magnetic fields, and ils very small or zero rest. Illa]>;; does not allow
us to use mass measurements to observe its emissiotl or capture. In fact the neu-
trino eludcd direct observation unlil 19.56, when C. COW3tl and F. Reines proved
beyond any doubt that it existed. Thcir expcriment. is explained in Example 8.6.
 >
Nuckar proaUtl (8.6
Unstable nuclei which lie above the stability region in Fig. 7- 1 can be considered
to have too many neutrons (or too few protons), and those which lie below can be
considered to have too mllny prot.ons (or too few neutrons). Thus we should expect
that these nuclei would attain stability by ejecting their excCS8 neutrons or protons.
However, this is lIot what happens- unlCS8 the nucleus is ill an exeited state-
because lIot enough energy is available fo r such processes (recall Table 8-2). What
has been observed is that clectrons and positrons are emitted instead. Therefore
we may :lSSume that a nucleus attains stnbility when, in fj- -decay, a neu/ron tran4-
forms into a pr%n nccording to the scheme
(8. 14 )
while ill fj+ -decay, a proton transforml i7110 a /!eulron according to the scheme
p ...... n +e++ ~. (8.15)
In the case of electron cnpture, the process is written as
p + e- ...... I\ + ~. (8.16)
III this way a nucleus may get rid of its excess neutrons or protons without actually
emittillg either of these particles. This theory of ,B-dccay was proposed in 1934 by
fenni. Equations (8. 14), (8. 15), and (8. 16) are compatible with Eqs. (8.11),
(8. 12), and (8.13), and express in a more fundamental way what happens in fj-
decay.
The above processes nllow us to infer another property of the neutrino: its spin.
The neutron, proton, clectron, and positron each have sl>in t. Therefore, in the
fj+ process, p ...... n + e+ + ~, the angular momentum 0 11 the left, ill units of h,
is i, while the angular momentum of n + e+ must be t t"" 1 or 0, depending
on whether the neutron and the positron have their spillS parallel or antiparallel.
Thus the neutrino mu.st ha\'e spin l, and be so oriented thaI. the lotal spin or angu-
br momentum of the three particles on the right add to t. In this way the law of
conservation of angular momentum is !llso saved! The same logic applies to the
two other processcs; (8. 14) and (S.1 6). This also explains the observed changes of
spin 61 of nuclei in ,B-decay. If the electron (or positron) and the neutrino hnve
their spins parallel (triplet states), then we hnve 61 = I or 0, but if their spins
are antiparo.ilel (singlet states), then 61 = O.
Process (S.14) hM heeu observed with free neutrons, since the reaction isexoergie.
In fact, the energy available is
Q = 931.4S [m n - (m p + m. + m.)J i\'leV = 0.7834 MeV.
Free neutrons decny acco rding to E q. (S. H ), with a half-life of 13 min . This is one
of the reasons why free neutrons do not exist. Free neutrons, shortl y after they
are produced, are either captured by other nuclei or disintegrate into protons,
electrons, and neutrinos. On the other hand, processes (S. 15) and (8. 16) are endo-
ergic, as the student can verify by computing lheQ-value for each process; therefore
b
8.4) ada decay J45
free p~tons are stable to fj-deeay, which accounts for the existence of hydrogen.
Othef\I'ISC all hydrogen would have disappeared, either by capture of the orbital
electron or by disin~egration of the nuclear proton. Processes (8. 15) and (8.16),
hOll"ever,.can OCCU.f 1II mor:c c?lllplex nuclei, when the required energy is supplied
by the difference III the bmdmg energies of the parent and the daughter nuclei.
However, neutrons bound in nuclei do not in general disintegrate spontaneously
~u~ the presence of the other nucleons may make the process energetically
ImpossIble. For that reason most neutrons in nuclei nre stable.
Beta decay illustrates t.wo fundamental facts of physics. One is the importance
of eonscrvation laws in analyzing processes that Occu r in nature. The other is the
variable nature of the fundamental particles. That is, fundamental I>articles, al-
though they have well-defined propertics, are not permanent structures and one
particle may change into seLS of the others, lI'ithin the limitations im~ by the
c?nscn:'ation I~ws. This is a radically new concept which was not contemplat.ed
either III classical or quantum mechanics. The illterrelntional character of the
fundamental particles opens nil entirely new vist:!. of ideas about the structure of
matter. In Chal>ter 9 wc shall explore this new /:li ~uation in greater detail.
A complete and satisfactory theory which Can /lCcount for all the transforma_
tions among fundamental particles has not yet been developed. It is ass umed that
processes such as (8.H), (8. 15), (8. 16), and others (which will be described in Chap-
ter 9) nrc the result. of a different interaction, callc<1 the u:eak in/eradion. From the
!lnalysis of the half-lives and energy distribution of ,B-emillers, it hftS been estimated
t~nt the strength of the weak interaction is of the order of 10- 13 when compared
WIth thnt of the strong or nuclear interaction, or libout 10- 11 when compared with
the electromagnetic interaction. At. present both strong and weak interactions
provide chal~enging.and exciting areas of research for the physicist, lind, presum-
ably, they Will continue to do so for many years to come.
EXAMI'J.E 8.6. Analysiot of thc Cowan-Reines neutrino-deteetion experiment.
Solraiotl: When an antineulrino is captured by a proton, B neutron and II. positron are
Produced; thnt is,
V+I>-+n+e+. (8.17)
This process of antineutrino capture may be related to Eq. (8.15) in the same wny as the
elee.tron capture process, Eq. (8. 16), is related 10 Eq. (8. 15).
N~clenr r~actol"ll prod~ce large numbel"ll of Jj--emiltef"$, which are the product.!! of
urnlllum 1iS!lOn (see Se<:uon 8.5), nnd thus nuclear reactors :lore copious sources of anti_
neutrinos. If t~e antineutrinos frolll a reactor fall on hydrogenous material, process (8. 17)
may take place.
T.h~ I~itroll can be d~tected because it lIIay collide with au clectrou, resultiug in the
anruillla.(lon of both part~cl~ :Ion.d the emission of Y.raya (Section 0.3), which can be easily
detected by means of 8cllltdlatlon counters. (See Appendix VI I.) One can detec~ the
nelll~n by ~ddin~ cndmium 10 Ihe hydrogenous substance. Neutrons-after being alowed
dO"'n III thClr motion through the substance on aCcQUlII of collisions ... ith other nuclei-are
ealltured by the cadmium nuclei "'ilh the emission of some Y-rays. This chain of event.s is
 pi

(8.4 Bela decay 347

346 NudtfJl' prOJ8tl 8.4)

Inddcnt un t incutr;no or, transforming into IItomie masses,

Q,+ - (,\I: - ,\Iz_1 - 2m,,)c: 2. (8. 19)

*(ntilbli(>n
rountcr Finally, for electron capture (Eq. 8.13),

Qoo - (.I f % - ,\I z_l)c 2 (S.2O)

T"'Kct I"'I~
with ..."d",;",,,
Thus, whenever the atomic mass of a given atom is larger than thllt of either of the two
neighboring isobars, it will decay by either p- or electron capture. Ho .... ever, for 13+
N1n1iILII'Ofl decay, the masses must differ by at least 2m. (about 1.097 X 10- 3 amu or 1.022 MeV). It
rountcr is suggeste<lthat the student cheek these rules by looking at 8Cveral groups of isobars in
a table of nuclides. In writing these equ!ltion~, we ha~'e neglectcd the effect due to the
binding energy of the electrOJis in the &.I,oms. The energy Q is shared (as kinetio energy)
Fig. 8-13. Schematic diagl11rn of the ncutrino detection c~l~rimen~. The incoming by the decay products. If we neglect the recoil energy of the daughter nucleus, then Q
neutrino reacts with a proton at I. The ejected positron anmh!llltc~ wllh an electron at also gh'cs the maximum kinetic energy of the electron or the positron in Eqs. (8. 11)
2 and the neutron is csptured by a cadmium nucleus at 3. and (S.12).
Let us illustrate these iml)()rl&.nt rules wilh some examples. The nucleus 14 C diilin-
tegrates into 14 N according to the scheme of Eq. (8.11), giving off an electron and a
depicted in Fig. 8-13. There is, of course, a delay of .seVCr!l.11~i~r~col\ds \.Jctwcc~ . ~he neutrino. The masses of tho atoms are M z ('~C) - 14.007682 amu and MZ+I (UN) ..
production of the 'Y-rays rCl!ulting from the electron-pOSItron ann~llI\al1on and the cnU!;Slon 14.007515 amu. Therefore Eq . (8.18) gives Q,- _ 0.000167 amu or 0.1556 i\TeV. The
of the 'V-rays resulting from the capture of the neulron by cadmIum: By mcan3 of, propcr observed maximum kinetic energy of the ejected electrons is 0.155 "leV, which is in
electronic circuitry, the two sets of 'V-rays are identified. An. analysLiI of the expenmental excellent agreement.
results provides convincing evidence that the assumed cham of events ha.s taken. lliace Next let u~ considcr the deellY of IIC into liB, according to the sc heme of Eq. (8. 12).
and that antincutrinos lire IIclUally coming from the reactor. Se\'eral other experlmen~ The ma.ssesof the two atoms involved are .Ifz (II C ) _ 11.014!)2amu and "'Z _ I (liB) -
have confirmed the neutrino hypothesis. In the Cowan-Reines experiment, perform ed 111 11.01279 amu. Thus their mll.~ diffcrence is 0.00213 amu or 1.9351\1eV, which is larger
an underground room below one of the reactors at Savanllah ~iver, the alltineutrino flux than 2m. or 1.022 :'IleV. Therefore positron emission iii possible with
w~ about .. X 10 ,6 cm- 2 8- 1 and the number of eventa reglst~ red \\'~ about three per
hour. It is considered that the neutrino flux on the earth, oomlng mainly from the sun, Q,+ - l.9S5l\1eV - 1.022l\1eV - 0.963 MeV.
iii about 4 X IO IO cm- 2 s- l .
The mell~ured maximum kinctic energy of the positrons observed in thi! decay is 0.06 MeV,
EXA MPLE 8.7. Determination of the energy available for each of the .B. .decIIY procel)Ses again in excellent agreement.
described by Eq!. (8. ll), (8. 12), lind (8.13). Finally we eOllllidcr the decay of 7Be, wh<e mass is M: ('Be) - 7.01915 amu. As
explained before, 71le is found to decay into 7Li, whooe mass is MZ _I (7 Li) _ 7.01822amu.
SoluLion: Let us first consider.8--decay, Eq. (S.ll). Initially we have a nucleus. of atomic Their m&iJll difference is 0.00093 amu or 0.866 :>.leV. This is less than 1.022l\1eV, and
number Z and mass m%. At the end of th e process we have a nucleus of atomic number therefore pooitron emission is impossible. The decay therefore occurs via electron capture,
Z +
I and mass 111%+1, plus an electron (mass m.) and II neutrino (zero mll.&l). ThUll the with QJ:X; - 0.866 MeV.
encrgy availllble for the process ill
EXAMl'LE 8.8. Calculo.tion of the shape of the energy spectrum in l3-decay.
Q~ _ _ lmz - (IIIZ+ I + m.)Jc2 - (IIIZ - IIIZ +1 -
2
1II.)c: .
Sol .. 'ioll' COllllider a large number of .8-radioaetive nuclei. We observe the emitted
Normally one uses the atomic masses .lIz instead of the nudcar masses, such that Mz electrons (o r pos itrons) during a certain time interval. Let us designate by dN the number
+
mz Zm. Making this substitution, we get of electrons (or positrons) emitted with a kinetic cnergy between E .. and E.. dEh. +
Our puq)()SC is to calculate dN /dE h , which is the number of electrons (or positrons) per
(8 .IS) unit energy mnge. We shall designate the kinetic energy available for the electron and
the neutrino by Eo which, if \I'e neglect the recoil energy of the daughter nucleus, i!J prac-
For p+-decay (Eq. 8.32), we have tieany equllito Q. Then Eo - f:h + E... Obviously '0 must be equal to the maximum
kinetie energy of the electron. When the kinetic energy of the electron falls \I'ithin the
range dE.., that of the neulrino falls in the interval dEb - -dfi.'... After the decay we
 p
Nue/tar prQuut, (8.5
348
may treat the electrOlland the neutrino as free particles enclosed in II vcry large IJOtcntial
box. Thcn dN I dEn must be prolJOrtional to the number of electronic states per unit.
energy range [that is, g.(Eh)[ nnd the number of neutrino states per unit energy range
Q.(f.'to). That is, dN I dE n ..... go(En)g.{E to} . From Problem 2.11, we have Q(p) dp "" p~ dp,
and therefore
g(1':) _ g{p) dpl db' ..... p2 dpl dE.
For a neutrino haviug zero rCij(. nl9.a8, the energy-momen tum relation is p. ,., Rtolc.
Hence
For nu electron (which must be treated relativistically), the energy-momentum relation
is En _ cv'm~cz+p! - "I"t~. lienee
Therefore we have
(8.21)
where C is a constant of proportionality "'hich delK!ndll on &everal otller fllclors in\'olved
in the tJ-de<:lIy, such as the IItomic number Z of the decaying nucleus and the strength of
the weak interaction responsible for the decay. It also has some delK!ndence on the
electron'" energy. Plotting dNldEn against En, we may compare with the CXI>erimentnl
resulls shown in Fig. 8-11 (a) lmd (b). The agreement ill general is rather 6Misfa.ctory.
We may note that Eq. (8.21) has beell derived on the flS:lumption that the neutrino has
a zero mZlSil. Howcver, if the rClit mZlSil had not been sero, wo would ha\'e obtained a dif-
ferent re~ult. Therefore the eXllCrimcnlal eonfirmMion of Eq. (8, 2 1) is Iln indirect proof
that the neutrino has a negligible rest mass. Given the degree of accurney of present ex-
periments, we can say thlll the rest mass of the neutrino must be less thlln O.OOlmo, nnd
therefore it can safely be taken as Icro.
When t\\o nuclei, o\'ercomillg Iheir coulomb rep ulsion, come very close together
(within the range of lhe nuclear force), a rearrangement of nuclcons lIlay occur.
This may result. in a nuclear reaction, similar to the rearrangement of atoms in
reacting molecules in l\ chemical reaction. Nuclear reactions arc usually I)roduc<.'<i
by bombarding a ta rget nucleus (M,) with II nuclear projectile (m,), in most cases
a nuclcon (neutroll or proton) or a light nucleus such as a deuteron or an alpha
particle. Heavier nuclei arc not generally used because the electric repUlsion be-
tween heavy nuclei re(luires a projectile with a large kinetic energy. Sometimes
photons nrc used nil projectiles. :-'Iost of the reactions result ill the SlIme pl.lrticle,
or anOlher p3.rticle (m,) being ejected and n residual or final nucleus (M ,) being
left in its ground stille or in 1111 excited litate. The rel.lction is designated by
the symbols M ,(1111, III,)M" where the initial and final nuclei are to the left lind
8.5) Nuclear reaction' 349
~o ~he right of the p3.rentheses and the incoming and outgoing light particles arc
lIISI~e the pmenthcscs. For e....ample, when \\'e bombard I:X with a- pllrticles
(or 21-1e), the result mllY be a proton (or lH) Ilnd a residual 170 nucleus. This
process may be II'rit.ten ill the form 8
I~N + ;He -+ lR + lio,
or in the more abbreviated notation HN(a, p)I7O.
In geneml,. when Ihe energies of, the pArticles involved nrc !lot too high, a
nuc.lea~ re~ctao!l supposedly occurs III two steps. First : an incoming particle or
proJccllle ~ ca~t~red, r~lIlting in the formation of an 1'niermediale or compound
lIIuleU& whIch IS Ln 0. ~lIghly .excited state. In the SCC()nd step, the compound
nucleus may be de-cxclted, eIther by emission of the S-.'lme incoming particle or
by some other means. The above example can thus be writtell in the form
I~N + :He -+ II:F,- -+ IH + lio,
where I: I~ is the intermediate or compound nucleus. The nste risk is to indicate
that the nucleus is in an excited state.
Generally speaking, to Il given first step in a nucle3.r reaction, there arc several
modes of dc-exeitaliOIl for the compound nucleus. Eaeh mode is ealled a ~chnnnel."
For example, when n Al is bombarded with protons, several products res ult some
of which are listed below: '
+ ;t Ie
H!I'I g
gAl + 11:1 -+ H!Sit -+ ~!Si + n
( ~!Si + l'
ftNa + 3l H+ n
Some nuclear reactions eannot be described by means of the compound lI ucleus
model. One exnmple is the 8lrippill(J rlac/ion,
HIHg + fa -+ lH + gMg,
or g:-'Ig(d, pg~i\lg. Experimental evidence indicates that in this process, when
the ~euteron con!es very close to the nucleus, the neutron is cal>tu red and the pro-
ton IS repelled Without the formation of a compound nucleu.~.
Nuclear reactions arc cssenti3.lly collision processes in which energy, momentum,
angular momc~tUlIl, number of nucleons, and charge mwt be conserved; lhe meth-
ods of newlollian and relativistic mech3.nies nrc used to compute some of these
quantities (~ Appendix I ~ ). If the incoming and outgoing particles are the SlIme,
the process IS called 8ca/lU/Il(J. Scattering is elastic if the lIucleus is left in the sUllie
s~ate, so thnt kinetic energy is conserved, and iI/elastic if the nucleus is left in a
d~fferent state. I,n t~e inelastic case, the kinetic energy of the outgoing pa.rticle
dlfTers from the kllletic energy of the incoming particle.

351! Nllcltor prOUJUJ
The Q of a nuclear rcnction /If i(m;, mJ)M I is given by th ~ expression
Q = 'CM i + til,) - (.11 1 + m/)Ic~.
In the ftbove eQuation ntomic m:lsscs are always used. If Q is positive, thc reaction
occurs at nI l values of the kinetic energy of the incoming projectile; but irQ is neg-
ative, mj must have aL lcllst Il threshold kinclic energy to produce Ihe rCllction.
As we shall see in Example 0.:1, the threshold kinetic energy of the incoming p..'lr-
ticle in the L-fromc of reference is
t,' = _QM/ + l1!i + m, + M,
k 2M i
if the particles must be treated rclalivisticll.l1y. However, if the particles can be
treated nonreiativislically, SO tlmtQ is Slllnll and HI,
+ M, can be replaced in the
numerator by i\l j + fII;, the threshold kinetic energy of the projectile in the L-
frame of reference is
b't= _ QMi +m;=
/II .
_Q(I + !II;til;).
This is the c.xprcssion used in most eaSC5.
In some cases the projectile is captured but no new p..'lrliclc is emitted. Ins tead,
a gamma ray (or photon) is emitted, whose ellergy depends on several f:letors,
such as the st:lle of the resulting nuclcus and the binding cnergy plus thc kinctic
energy of the captured I)''lrticlc. An example of a capture reaction is 21 AI{Il, 1') 28 t \1.
Another is the capture of a neutron by hydrogen in the reaction 11'1 (n, 1') 21-1 i the
resulting iltom is deuterium. The reverse process may also occur: a nucleus may
absorb a photon or 1'-ray whose energy is s ufficient for a particle to be ejected.
This process, which is equivalent to the photoelcctrie e!Teet in atoms, is called a
p}wumuc/ear reaction. Ex:mlplcs arc nj\ lg(1', p)2~i\a and 211 (1', n)'H.
A nuclear reaction may 00 dC!!Cribed in terms of a eros, &ecti(m. The concept
of cross section was introduced in Sections 1.9 and 7.8 for certain processes. or
course, for each l)'' lrtieular nuclcar reaction, there is olle eross !lCCtion, which is ex-
pressed as a function of the energy of the projectile or incoming particle. Cross
sections arc defined experimentally in the following way. Suppose that a s:unplc
of thickness'::";!: (where.::.,;!: is small) and arca A , containing 11/ target nuclei I>cr unit
volume, is exposed to a current density ".11 of incoming pnrtieles (of t.ype a) per
unit area and unit time, where nd is the number of incoming particles per unit
volume and t> their velOCity. Given that N. outgoing particles (of type b) a re ob-
served [caving the snmple per unit time, the cross section for the reaction (a, b) is
N.
O'(a, b) = (n~")(I1/A /U) .
This definition coincidcs with 10:<1. (7.16), since 'iitl ;u is thc tOtll[ nUll100r of target
nuclei and thus N6/ (II/A 6.x) gives the total nux I>c r unit time of outgoing particles
pi
(S.5 8.5) Nuclear reat/iO/1f 351
pcr target nucleus. We note thnt N6 is expressed in S-I, that ll aU is eXI>rcssed in
-, , - I -2 - I hI .
(8.22) ~n ;11 . o r m. S , t at Illi j,;!: IS a ullIlless numoor, and th"t 0' is expressed
111m !l.S III l>rcVlous cases. i\lost cross sections nre of the order of R'l _ 10- 28 m2
where Il is lhe 1.l\lelen~ radius. The (Iwullity 10- 78 m'l is called " baril, abbrevi:
ated b, ~ mentioned HI Section 7.3. It is a unit commonly used for expressing
cross sections of nuclear processes. A submultiple i.~ the millibarn, mb, equal to
10- 31 m 2
. For a g:vel,~ incoming pn.rtiele a, there m:ly result severnl differen t outgoing pnr-
tlcles b, b, b , corrcspondmg to the seven,1 reaction channels, each II'ith its own
cross section O'{a, b), O'(a, b'), etc. The lob.! reaction crose section for particle (I. is
t hen
lI'(a) = O'{a, b) + O'(a, b') + O'(a , b") + ...
The pilrtbl and total macroscopic cross sections of a givcn Sllnlple are defined by
~a 6 = II/O'(a, b)
and
2: n = 7I/O'(a),
(8.2-1)
and both are expressed in m- I .
T~e cross. section for ench nuclear reaction depends on the energy of the in-
cOlllmg particle. In many nuclear reactions the cross sections exhibit very pro-
noun~cd .peaks called rnonallce8, corresponding to energiCii at which the pnrticular
reaction IS more favored or probable. These resonances lire closely related to the
energy levels of the compound nucleus. Figure 8-14{a) and (b) s hows the total
a?d capture c~ sections for neutrons in nluminum in terms of the ncutron energy.
Figure 8- I4 (e) gives the erQS8 section, in nrbitrnry units for the nuclear renetion
31CI(p, n)31 A as a function of the prolon energy. From tl:e analysis of such curves
we can obtain extensivc information about. nuclear structure and energy states. '
I n n)[IIlY cases the nucleus which results from a nuclea r reaction is unstable or
l1'Idio~ctive. In fact" it is through nuclear renctions that the artificially radioactive
~lUclel arc formed. Artificial radio.'lctivity 11' !l.S discovered by F. .loliot and I. Curie
11\ 193-1, wh.ile they II:ere stud yi ng nuclenr reactions produccd by bombarding light
clements With a-partICles. One of the reactions they observed was
19B + ~He __ [11Nt __ IW + n.
The nucleus LiN is unstablc and dceays according to the schellle
IW--I~C+e++v,
Another interesting series of rcactions are those resulting frolll combined neu-
(8.23)
~ron capture nnd .B-dceay of the uranium isotopes, producing new nuclei with
Z = 93 (neptunium), Z = 94 (plutonium), Z = 95 (americi um), and so on up to
Z = 100. The partial chain of reactions is shown in Fig. 8-15, where ench hori-
wntal arrow represents n neutron capture nnd ench vertical a rrow a .B-decay.

352 Nu.ckor pt'OCl$fll (8.5
8.5) Nu(/t(lr ,roc/ions 353

" ' 00
f jHIe<:'ay
~~lFm

" _ n-<'1lp'''"' =F....

~Je("tron ('-.lpl"'"
\0 ,99
~ :.10('[

(.)

.2
II
8
7
i 9S
,~ "00
,

2 11("",
Zi~I~k
2:13(:f

! , 2.to"
~ ~H .\",

~ " ~nl'\I
2'~ 1'1l
~
3 "
2 2<,
, '" '" '" '" ~[WIII number, .1
'50 2:>2 2.';.1

" '" '00

'''' 200 2'" 300
Neutron energy, keY "" "" .'" "" Fig . 8- 15. Nuclear reaction sequences fo r production of heavy nuclides by slow neutron
irradiation of 239PU.
2Q
E
.- AttcIl1L1Iotion of n beam of llarticicll of type a llS
'i '"
XAMPI. S.9. II. function of t he dis-
tance:t trnvcf!!C(! in II target.
" 3

,! "
(b)
Salutio'" Designating by I - a.v, the incoming current density of partic!e.'! of type a

8 , falling on a layer of thickness lI.:r, we h!l.ve from Eq8. (8.23) and (8.2") that
"
~
'-'
gives the number of particles removed per unit area and per unit time from the incoming

" ,'" .., .'" bellm; in other words, i~ gives the deere:lSC in the current density of the proje<:tiJes, which
mll8t be designated by - 61 since 61 is negati\e. So we mill' write
'" "" 200 250 300
NeUlron energy, keY "" ""
tJ./ - - /'::. 6%. (8.25)
20
!,. If the thickness tu: i!i vcry small, " 'C may write instcad
,"
'g dl _ -I"dx

~ "
" Integrating, and designating the incoming particle ftux for
dIl l - - 2: d.l:.

% - 0 by 1o, we obtain
:
<
" I '" loe -'!~.
(,) .,.- \0
(8.26)

~ 8
, We may use this equation to dc tcrmine2: aftcr mcasuring 10 and I. Oncc wc know 1:, we
obtain II by using Eq. (8.24).
~
)w
b
u

:~ \...
,82Q
"'"
U
''''' loSS.
Proton ~ne'l(Y. kc"
""y
''''"
0V
HI'lO
.. Fig. 8-1 ,1. (a) T he total and (b) the capture cross section of aluminum for neutrons
1\8 a fu nction of neutron encrgy, [Dsta from n.. lIenkelnnd II . llargchall, Phil', Rev. 80,
145 (1950)] (c) CrOilS section for the reaction 37CI(p, n) alA 0.8 a function of proton
cncrgy. [Data from Schoenfeld, Duborg, Preston, Ilnd Goodmnn, Phy" ReD. 8:>, 873
(1952)J

J5~ (8.5
t.X ,jMIU~; B.IO. DiscoHry of the neut ron,
Sol",;o.. , An interegting and histori cal allplicalion of the conservation law8 in nuclear
proces.~C" i~ the ~tory of the discovery of th e neutron. In 1030 Bothe and Beeke r ob.scrvOO
that whcn they bombarded boro n and beryllium with a-pnrticles, a highl y penetrating
radiation II'a~ produced . This radi'ltion W/13 not composed of charged particles heCIluSC
it wa.~ not IdTcctcd by electric or mngnetic fidd~. ,",or thllt rCRI;on thcy thought tha t the
radiation cO Il.'i~ ted of high-energy l'-rZl)'~, lind they wrot e the reaction M
:Bc + ~Ht' ........ Ilk] - I~C + 'Y. (S.2i)
The Q of th i~ reaction is lOA '\leV. Since t he kinetic energy of the a-particle i$ about
S :\leV, the total energy al'ailable is 14 .\ lcV in the C)I frame of reference. This energy
mu.st he shared by the I~C atom and t he "I'-pholon. Thus the "I'-ray~ should have an
cnergy alightly 1C$l! than 14 '\leV. From nb.!orption mea.sureillents it wa.~ esti mated that
the I,hoton energy should he abou t 7 :\[eV. Two yea l1l later {1 932J Curie and Joliot Qb
lIC rl'ed tlll\~ wh~n the mdiMiol\ from the l\bo,'e reaction ptlS!ed through l\ hydrogencous
material, highly energet ic protons were produced, with a maximum energy of about
7.5 ~ l c V. The natural intcrpret tLtiOIl WllS to n~ume th!!.! the protons h(ld bee n knocked
out by t'(ll1i~ioll with 1'-photons prodllced in the above reaction, re.<ulting in a (1', p)
nud CIIf ("Omptoll effect. The most cnergetic protons result frolll a heAd-on ro llision in
wh ic h the photonll recoil or llre dcfiect<:'d 180. Gi-'en that E~ and p~ - h'~/c flrc the
energy and momentum of the inddent photon, E; and p; - I~;/c those of the reooil
photon, and f;~ and p - ./2m~f:~ thO!!C of the proto n (wh kh mlly be treated nonre1::t.-
li\'L~tiellllr), the con.."en'lItion of ellcr)::")' lind momentum give
from "'hi cb lI'e mny get
In;<<>rling the maximum v:lllle of E k , 7.5 '\leV, and recalling that Ulpe2 i~ about 938 .\leV,
lI'e then get I~~ ~ 6~ Mc\'. This I'lIlue of the "I'-ray photolls is much huger than the
energy :ll:lila\.Jle from the re9.c tion, gh'en above as 14 Me\', or that deduced from abSQr]>-
tion measlll1'nlellts. ',"hat is 1I'0r"4', (,,()ll~id ... ring the effect of the products of the He-He
reaction on other ~ub;;tanCCll, we obtain other ,'alues of 1..\ , in some cases sa high as
90 :\leV. Therefore we can obtain no consi~tenL results for E~ from Eq. (8. 27), co m-
l)1uiblc with f'nergy And momentum co n'ICrvntion.
J n 1932 the British physicist J. Chadwick sho wed thM all these diflicultiC!S disappeared
and the eongcrl'ation i:t.ws lI'ere resto red if, instead of 1'-rays, neutral particles were
emitted, hal'ing II llW.SS dose to \llI\t of protons. These neutral jWlrtieJes were caUed neu-
trons, I\I\d the process can now he written J\S
~Be+ ~l:I e -> It~CJ ' ...... l~C + bn. (8.28)
Chach"iek made careful measurements of the kiuet ic energy of protons and nitrogen atoms
knocked out by the neutrons when they were passing through II. substan ce cont:..ini ng
hydrogen and nit rogen, respeet iwly. This allo"'OO the massQf the neutron to be calcula ted,
8,5) 355
re~ulting in fI value between 1.005 and 1.008 amu , which is I'On~i81 ('nt with the energies
iu\'olled in the abo,'c. reaction. Later on, more preci.sc mcn~urernen t8 yielded
InR - 1.008665 amu.
Chfldwic k!~ experiments were the foundation of OUT l)resent model of the nucleus Ii
model whi ch !\Ssume8 that lhe nucle\l~ i~ compo.'5Cd of prQton~ llnd neutron~ . I'rio.'lo
that time 8cientists conaidcrcd nu clei as heing cornl.lOSe<i of ])rolond and electrons (A
protons and A - Z clcctron~, or to tOlal of 2 .-1 - Z particles). But thut fI~urnption
.rsulted in insnrmountllbl Cl difliculticlI: cJcctron~ were too big comllll.ed wilh the nuclear
melill.', their magnetic moments \l ert' 103 limCll larger than Ilu clea r magnetic moments,
find their ])te5encc inside II nucleus made it impQssible to accou nt for the oi.lscrl'ed \'alu e:J
of the nuclear spi ns. Thus the timely rC('ogllition of the neutron was more tha n welcome.
t."XAM I'I. 8.11, .\ s.hee t of gold 0.3 mm thick is eXIMlsed to a slo"' neu tron current
den5it)' of 107 neutrons em- 2 s-'. The eallt ure eroS!! seetiQn of 1&7Au for lhermal neu-
trons is!H X 1O - 2l1 m 2 The dt nsit)' of gold is HI.3 X lOa kg m- 3 and its atomic ma.ss
is 197.2amll. Find the numher of nuclei of 1~8 Au formed IlC r seoo nd and IlCr cm 2 of the
sheet, according to the reactio n 197 1\U (n , 'Y\ I98Au.
Sol"'io.. : Let u.~ de..ign.'l.te the capture cross section of I&7Au for thermal neutrons by
<7(n, "I'} and the numher of a toms of gold per unit volume by nAu. Then th e ml\ croscopic
croSlisection for neutron capture, according to Eq. (B.24), is 2; _ 1I,,"a(n, 1'). Gil-en that
10 is the incident neutron curren t density, the numher of neutron~ that have not been
captured after a distance x, according to Eq. (8. 26), is 1 _ I ~-%'. The number of neu-
trons that hal'e been captured in t he di..stll.nce x i$ thus
10 - I - 10( 1 - ~-%~).
This is equal to the number of IIIIIAu. nuclei formed. In our case,
19.3X!0~kKm-3 ~8 -a
197.2 lim\! X 1.00 X 10-27 kg nmu I - 5.89 X 10 m
is the number of 197'-\11 ntoms per 11\3. Thus 2:: _ 11.An<7(n, 'Y) _ 562111- 1. Setting
;t - 0.3 mm - 3 X \O - ~ Ill, lI'e have~.t _ 0.1686 and e-%~ _ 0.845. Therefore
This gives the numher of neutroll8 Absorbed and of 198:,U ato~ formed jlCr em 2 and IlC r
6Ceond.
I-: X/lMI' U '; 8.12, Determination of the energy le\'els of 28Si by use of the nuclear reac-
tion 27 AI(p, (1)21 :\{g :..nd its inverse, 2~ .\{g(Q, p)27 A!.
Solutio", The compound nucleus of the reaetiOll 27:\I(p, arp ~ i\fg i$ 28Si, so that we
rna)' write
It is expected tha t th e cross ~ Iion for this reac tion will sho w mar ked IlCaks (i.e., reso-
nAI\ CeS) when the total cnerlty in the C-frame Qf reference of the system 27 Al + IH
min us the rc;t-ma.ss energy of uSi coincides .... ith the energy required to elleite 2 Si to
 p

356 Nucie(Jr prouut. (8.5 Nuckor flS,ion

8.1i) 357

where Eh ill noll' the total kinetic energy of the sys~ m (0', 24Mg) in the C-frame. The
diffcren t energy relations /1rc sketched in Fig. 8- 16(11.).
-.- - From our discussion it is clear that the cross 8elltions for the rC/1ction 27 AI(p, O'F4Mg
and its inver.!C, ~4Mg (a, 127AI, mUllt show t he I!IL mc set of resonanccs. 1I0\\'ever, for
each rC80llance the kinetic energy of the system (0', ~4Mg) is uniformly larger than the
kinetic energy of t he system (p,21AI) by the amount (11.588 - 9.990) MeV _ 1.598
'990 w
71:'1 1,: + 'I I..
,
, MeV whell the energies are referred to the respective C-frames. This eonclUJ!ion is eon-
firmed by the experimental results shown in Fig. 8- 16(b), which gives the ero$!! sections
, for protons with energies from 1. 1 to 1.8 MeV find for a- particles wi th energies from
2.7 to 3.4 MeV. T he result constitutes a satisfyillg verification of the compound nncleus

20
'") LJ' eoncept, lln d serves to show the origin of resonances in nuclear reaction~. Thc energy
levels of 288i, in the energy region considered, can bo determined from t he energies of the

.LL
lleaks shown in t he figure.
"
W
,
1.3 f.4 An im l>ortant nuclear process isjiuiOll. It consists in the division of a heavy nu-
" cleus, such us uranium or thorium, into two fragmcn ts of comparable sizes. Fission
a., e
a natural process is very rare 311U is believed to fission spontaneously with a

.. 3

2 ~1:\[~ ...pFAI
half-life of ap proximately IO U years). The usual method of p roducing fi !S.<;ion a rti-
ficially is to excite the nuclell.'!. The threshold or minimum activation c nergy re-
quired fo r fission of a heavy nucleus is from 4 to 6 )'1eV. One o f the most effective

27 2.' 2.9
\.,... A 30
,
3.'
" 3.'
J 33
1:',,-
means of inducing fission is by neutron capture. The binding energy of the cap-
tured neutron is, in some ca.<jCS, enough to excite thc nucleus above the threshold
energy, so that division into two frngments takes I)laee. This is, for eXll.m ple, the
Kinetic ~nel)(Y of inoominll: I~,rticle 1'1,,~ Inl")l;cl case of t he nucleus 2:~U, which u nd ergoes fission lifter capturing a slow (o r t.herrnal)
,,,,!'Ieu< in the ('-f"'tlle of ,eferen\"e neutron. Thc process may be expressed by t he cqUll.tiOll

."g.
'0'
8-16. E"ldeoce for the compound-nucleu.i eoneelJt by U!;C of the 1l'3ctions
27 AI(p, aF4~ l g and 2'Mg(a, p)27 AI T he compound nucleus IS 2&:51. (a) Energy rela-
~ions. (b) cross seetion for both reactions. ]Dat.'l from Kaufmann, Goldberg, Koester, and
For othcr cases, in ordcr for fission to take place, the neutrons must have some
Mooring, Phyr. Rc~ ., 88, 673 (1952)1 kinetic energy-of the o rd er of 1 MeV- in addition to the binding energy. This
is what oceurs wi t h 2:~U, which fissions only after cal>tu ring a ffUjl neutron. The
one of ib stationary states. This energy i~ reaso n for this different behavior lies in some details of the structure of the different
nuclei rclated to the (Xliring tc rm in the mass formula given in Eq. (7. 12). The
(.I r (nAI) + nip - M(28Sil ]c2 + E. p .. (11.588 + f: h ) i\[rV, nucleus ':~U is even-odd, wi th 143 neutrons, and when a neu tron is captured, an
where E is the total kinetic energy of the system (p, 27,1.1) in the C-frame. Once the
kp . + even-cvclI nuclell.'!,':;U, is formed. The captured neutron is paired with t he last
compound nucleus IS formed, It may break .mto the system 21:\, 1g a. T h e 24:\..1g may odd neutron of 2:~U, releasing the additional pai ri ng energy 6 _ 0.57 i\! eV. On
be in its ground slate or in an excited slale; the slale of the 2 ~ 1>lg nucleus determme8 the the other hand, ':gu is an evcn-cven nucleus, with 146 neutrons, all paired, and
kinetic energy of thea-particle and of the -r-rays obscn'ed whcn the 2~ Mg nucleus proceeds when a neutron is captured, a n even-odd lIuclell.'!, 'ltu, results, with no extra
to its ground sta te. The inverse reaction, that is, pairing energy availablc. I'or the same reason ';: Pu, with 145 neutrons, undergoes
2 ~ ;\Ig + 411e ..... [28Sqt ..... I H + 27 AI, fission by slow neutron capture. TlI.ble 8-3 gives l he excitation energy of some
nuclei resulting from neutron ca pturc and thei r fission activation encrgy; from
produces a 28Si nucleus with an excitfltion energy given by
th is information it is possible to deduee which nuclei a re fISSionable by ther mal
[.11(24;\lg) + 1II(4He) - .11 (28Si)Jc2 + t.'h - (9.900 + E_.l MeV, neutrons.
 ..
358 (\'uclror proc~lI$t$ (8.6 8.6} Nucit(lr fu.iOfl 359
T AUtE 8-3 FiSll;o ua b ilil y o r Ilea .",. N uclei with T h ermal
Ne Llt ro n ,

T' "
,.)-----/--.,,, '-'''':--_+_ Ex~iled ~1:l!C
Target COnlrlOund Excitation Thrc~hold
nucleus nu cleus e nergy, i\leV energy, MeV ( loi~" prob"bility
~nU
Hblj
[23 41iJ
[mUl
66 ...
5.3
,,
,
{If 1\"r1e,,~ (If fi:Miun )

,,,--
6.4
23Sr [23Dlj J 4.9 5.5
F33Th1
,,,
232Th 5.1 6.5
2JlPa F3~l'al 5.4 5.0
,
,,,
237Np [238Np[ 5.0 4.2
239 pu [2 40pul 6.4 4.0

,, ,.
T A ULE 8-1 ThrC>lh old En e rg ies ,., "L____~;L,______ ___'I;";',;,,=,,~"':,,::'"
J>h o to fi ssioll
Fig. 8-1 8. Po tential energy function for a nucleus under deformation.
P hotofission
Nuclide threshold,
l\ l e V
in l ~ig. 8- 1i (b) . 0 nee the excitation energy has been released ill the form of "forays,
~U 5.08 0.15 the nucleus retur n s to the c<]uilibrium shape, The process hM therefore OC'C1l a
=U 5.31 0.25 mdintivc neutron capture. When the l!.xcitation energy is larger, the nucleus is
""l' 5.18 0.27 deformed 1l10m , as in Fig.8- 17(e). Even ill this ease there is some l>robabiliLy that
Utl' u
UtTh
5.31
5AO
0.27
0 .22
iL may return to the originallihape after de-excitation by ')'.my emission. But if
the excitation enel'gy is large enough, the defom13.tion Illay be so Inrge that the
electrical repulsion betwccn the two halves is inrger than the short,..mnge nuclear
A nucleus IIlny also be excited enough to suITer fissi~n by flbso~bing 7-.rays of interaction, and there is a greater probability lhaL the Ilucleu$, instead of return.
encrgy equa! to or larger than the threshold energy reqUIred for fi~lon. '1 h~s proc- ing to t he sphcricnl s hape by rele:\Sing ')'rays, deforms more nnd morc until it
ess is called pliolojis8iol!. The thr!!shold energies for photofisslon are given III divides into LWO fnlgments- ns indicntcd in Fig. S-17(d)- resulting in fi ssion.
T able ~ for some nuclei . figure 8- IS shows schclllnticnlly the I}()tential energy of a nucleus versus its
deformation. For deformations smaller than a ~rtain criticnl value, designated D

o in thc figure, the nuclenr fo rces domi nate the electrical forces and the potential

o o,d,
energy incretLSCS wi th the deformation, resulting in the curve AB. This is the region
of stable oscillation s. For deformations larger than D, the electrical forces dominate
the nuclear forces, and the I}()tential energy decreases with furth er deformation,
resulting in eun'c B e, which corrcs.ponds to the division into two fragme nts; thesc
fragment s fly apart because of their coulomb repulsion. If 8 0 refers te the ground
}."ig. 8- 17. Deformation of a nucleus
according to the excitation energy. ,., (b ) ,,) st:l.lc of t he nucleu s, the fission thretihold energy is f.',. T his curve should be lakell
only in /l. qualitative sense.
If the nucleus is initially in n state with energy less thnn tlHlt at n,
'iUeh as
li'igurc 8- 17 depicts the supposed mechanism of nuclear fission. Con;>idcr II. 8 0 or H, it unde rgoes oscillations without fission. I t is prevented from spontaneous
nucleus whose equilibrium shnl)C is spherical, as in Fl,g. 8-,17(11.) . If properly ex- fi~ion by the potential b:lrrier. The nucleus may, however, tunnel through the
cited, it lIlay experience collective vibrations, as explruncd III .Sectlon 7.10. When potential barrier, resulting in spontaneous fission. The probability of tunneling is
the excitation energy is low, the oscillations about the s phcr~ea l ,shape arc sm~l, extremely low when the nucleus is in the ground state, so that spOntanoo us fission
80 that at its maximum deformation the nucleus adopts the elh]>SOldal sh ape sho n is a r:Hller iml)robable cvent However, the penetrability of the barrier increases
 - S.1i) Nuclear fiuiotl 361
(8.6
360 Nw;/wr proct!IuI

with the excitation ellergy of the nucleus, m:tking fission more prob..'Lble. If ,the
nucleus hM all excitation energy larger than E" it obviously undcrg~ fi SSIOn.
T herefore fission by neutron capture will occur if the binding energy plus the
kine tic energy of the captured neutron nre enough to take the n~cleus over the
l)Olcntiai barrier. As we said ,before, if t~lC binding energy, alone 1,5 e~\Ough, 51;.\\'
neulron fi Sl;ion OCClln;. For 23~U, the height of the potcnwd barrier I,S abou~;~.3
:McV ; thus .:i.3 r-.lcV is the critical energy required to produce t he fiSSion. of U
by ncutron capture. It is important to note, hO~\'evcr , tl~at the~ IS lIot It
si ngle threshold energy or a unique critical dc~o~n.mtloll; these qualltttH~ depend
011 the cxcit:ltion mode of lhe nucleus and thc Ilulla! statc 0. thc nuc~cUll.
T hc capture of :t ncutron docs not necessarily lead to fi SSIOn even l~ the ener~y
is available, because (as cxpl:lined previously) before the nucleus h.lL'l ll.me to.SP~ll,
it may releMC its excitatioll ellergy ill the fo rm of 1'-rays, rcsultmg In radw.llve
cnpture instead of fissioll. Therefore, when neutron C3pture W.kcs.pbce, two ~1l1- Thermal neut~

pcting processes enter into pby: radiative capture (n, 'Y) and ~sslon (I~, f}. Each 14_.\'eV neUlrons
of the- two processes is chamcteri1.oo by it.'! own cross sccllon----deslgnatcd by
O'(n, 'Y) and O'(n, f), respectively- which . dep<:nds, on the _energy of t he neu.tron.
T he values of these erOS!! sections are gIven Hl 1 able 8-" for neu~rons havmg a
"X) )2<) 1<0 ",) )00 )'" L6(l
,\1:\.811 number '\IM:! nu",ber
"elocity of 2"200 m ... - 1, which corresponds to the average velOCIty of thermal
(.) (b,
neutrons at room temperature. The last. column lists the average number of
ncutrons released per fission. Fig. 8-1 9. (II) T hermllll!.nd fast fission yield of 23.'iU. (b) Thermal fiMion yield of 23aU
and 230 1'". [Datil from S. Knteoff, NljCl~oniG. 16, No. 4, 78 (A pril 1958)J
TAIH.E 8-5 I'rope rli ce of Som e Fissionable MU le riu ls for
Ther mul Neul TOlls
We C:\l1 see th:l.t ncutrons are relessed in fiilSion by eXlIllli ning the stnbility region
in l~'ig. 7-1. For the henviC8t nuclci, such M umniulll, the rntio of neutrons to
Nucleus O'(n, r), barns O'(n, 'Y), barns protons is N jZ __ 1.55. This, of course, will be approximately the mtio for the
233U 525 53 2.51 rcsulting frngmcnt:;. Howevcr, from the sa.me figurc lI'e sec t.hat fo r medium-mass
stable nuclei the ratio is N jZ -- 1.30. T his meallS that the resulting fragment-s
~35U 577 101 2.44
have too many ncutrons, and thus lie above the stabi lity region. Therefore they
23&PU HZ 286 2.89 are p--rndioacti \"e. In fact, uranium fission is one of the methods of producing
P--r:l.dioflctive isotopes. Howe\cr, the neut ron excess is so large tha.t 1I few ncutrons
(Ire released at the time of fission. T he averagc number of ncutronti 1"CICfL'SC(l per
Fission is not 1\ symmetric pl'OCCSSj in general the two fragm~nts have unequal fission (designated :IS v) is givcn in Table 8-.') for !jome nuclides, assuming that
m'lSS numbers. T he most. probable division is into frngrnents WIth mass numbers fis.;;ion is induced by slow ncutrons.

around 9.1 und 135 as shown in Fig. 8-19, whIch . gJ\'CS
. " .
tIe . yle
ISSlon . ld 0 f 23aU ,
Thut energy is relelLSed ill nuclear fiilSion may be seen from the binding energy
~uU, and 23l1 pU f~r thermal ncutrons. T his can also be sec.n in Fig. 7-1, whe~c per nucleon, represented in Fig. 7- 5. For a heavy lIuclcus, the binding energy is
thc radioactive Iluclides abovc Ihe sbbilit.y region are partIcularly abundant III about 7.5 :\lcY I>cr nucleon, but for mediul\l-mass nuclei , corresponding to the
the rcgions around A = 00 and A = 13:\ :l.SSOCh.loo with N = ,'j() and N = 82, two fragments, it is about 8,4 ~lcV I>cr nucleon, resulting in fin increllSC of bi nding
rcsl>cetively. T he rCIl80n fo r this asymmetry seems t.o be the t.endency of a heav'y encrgy l)Cr nucleon of about 0.9 :'- leY, or a total of t"tbout 200 l\ [eV for nil nucleons
nucleus to s plit into fragments having closed neutron !Shells Hround the magIc in a ur~lIlium nuclcus. This, then, is the order of magnitude of thc energy liberated
numbers ,'j() and 82, respectively. . . in thc fission of a uranium atom. Thc energy relc-..t.SCd aPI>cars as kinetic energy of
Two properties of fission mnke it :. very important process for p.ractlcal nPl)h~~ thc fr:lgrncnlS, of the released neutrons, and of the disi ntegration products (that
lions: One is that ncutron' orc reiCll8e(l ill jiuioll and the Olher IS that Clltrgy III is, electrons, pilotOIlS, and neutrinos) resu lting from the p-decay of the radioactive
released ill ji88io1L
362 Nudtflr PNXlfU' (8.6
-
fragments. Since the neutrinos emitted in the ,B-<iccay (and !to few photons as well)
normally escape from the material in which fi ssion takes place, only about 185 i\ lcV
per atom can be rct:tined, an energy s till considerably larger than the energy lib-
e rated in a chemical reaction (which is of the o rder of 3 to 10 cV per atom).
For example, the energy relcMcd ill the fission of 23~U is dist ributed, on the
nvcmgc, lUi fo llows:
I\incUc energy of fmgmcll lii 167 MeV
Kinetic energy of fission neutrons .'i
Energy of 1'-r3ys (mdialoo at ~hc time of fission) 7 rcsu~t of lhe c~P ture ,o( a neutron by U6U is larger than the height of the potenti.sl
Ellcrgy of ,8--deeayele<:trons 5 bsrner for 1iS:>lon. \\e conclude then that the n6U lIucleus resulting from lhc neutron
Ellergy of "I'-dCCIlY of fragments 5 Cal)turc by 235U undergoes !iSlSion even if the neutron is so ~Iow thst it contributes a
Energy of ,B--decay neu trinos 11
T otal energy 200 :'.Io\'
T he exact. energy dist ribution varies, of course, from one case to anot her.
The (ac t t ha t for cfteh neutron absorbed ill o rder to producc one fission, more t han
t wo new neutrons a re emitted (on t he avernge) suggests the possibility of a cl!ai1~
reacliQI!. T hat is, if things ure arrilnged in such a way that, after euch fission, Ilt.
least one of the new neutrons produces another fission, and of the neutrons relrnscd
in this fission, again at least one produces a fission, and so on, then a sclf-sustailling
process or chain reaction results. (Chain reactions are very common in chemistry.
Combustion is a chain reaction. BUniing requires that a molecule have a certain
excitation energy so that iL can combine with an oxygen molccule. But once the
first molccules arc excited and combine with oxygen, the energy liberated is enough
to excite more molecules of the fuel, and burning results.) If in each stage of the
procef!8 more than one neutron per fission produces a new fission, the nUlnber of
lis.-;ions illcrenscs exponenti:tl!y :1nd n dive rgent chain reaction resulkl. ThiJ:l is
whitt. happens in an atomic bomb. But if, on t he a vcr:1.ge, only ulle neutron uf
each fission I>rod uees a new fission, a stendy chain rcne tion ill mainlnined under
controlled conditions. T his is whnt hnppcm~ in !l nuclear reaclor.
I n jM/nuclear reactors the lIeutrons nre used :\t. the sn.me energies ( I to 2 :'IleV)
at which they are released ill the fission process. But in lhermal nucle:u reactors
the neutrons lire first slowed down by allowing them to collide with the atoms of
some other substance, called a moderalo" until they come to thermal equilibrium
with the substnnce. T he neutrons arc then called thermal. The moderutor must
be a subst:mee which has small mass number and a small neutron cnplure cross
section. Wate r, heavy water, and gmphite are the sub.<;talicCi! most used as
l\1oderators.
The energy releascd in n nuclear reneto r is extracted by menns of a circulating
fluid called a coolani. I n power reactors this energy is used for heating or for the
gcneration of electric power. In rC5Cllrch reactors the neutrons are uSl'!<i for dif-
feTent kinds of experiments, or for isotope production.
EXA M I' I.": 8. 13. Determination of the energy released when a neutron is captured by
233U and by 238U and the fe&.!libility of fission of n~U and 238U by thermal ncutrons.
8.7) Nuekar JlUiOli 363
Sol,,'ion ; TheQ (or the capture rc~tion of a neutron by an atom of ffill.'lS number ." i~
Q = (JI" + m~ - .11 "+I)e 2 - 931.48(M" + rIIn - '\/"+ 1) i\ leV,
wher~ the masses in the second CXtlrellSion must be e.xpres!lCd in amu, and all rcfer to
Il tOnllC masses.
CoII.'1idcring the C:lSC of ~J~U, whidl becomes noU after eapturiug a neutron, we ha ve
.1f"eafjU) - 235.1170 amu and .11 ,,+1 (2J6U) ~ 236.1191 amu. Using "'0 _ 1.0000
amu, we find that Q - 6.43 :'IleV. 011 the other hand, the potential barrier of n6U
for fi~~ion is about 5.3 :'I leV. Therefore the excitation energy of USU formed 9.8 a
negtigible kinctic energy.
Con~idering the ease of 238U, "'hirh becomes n9U after capturing a neutron we h3ve
.If,,(
238
n- 238.12.\9 amu and ,II "+1 (nuU) - 239. 1287 IImu. '('hut the Q 0; the rllp-
tllr(' r('action ii 4.85 .'IIcV, which i~ ~ 1ll1lJ!er than the height of the fillSion barrier of 239U
by about O.6i\1eV. Therefore, 1I11lcss the cliptured ncutron has ~umcient kinetic energy
to Ulake lip for the Cllergy required, fi,s,,:ion is not produced. Experimentally it is found
that the millimllm lliboratory kinetic energy of the neutrons must be about 1 nleV to
fission 2~8U.
11.7 i' -"clf! flr "'''Nion
A process which is the reverse of nuelea r fission is nuclear JUJIioli. It consists in the
coalescence of t\\o colliding nuclei into a larger nucleus. Bccause of the coulomb
repulsion bet.wecn nuclei, they IlIUst have Il certain kinetic energy to overcome the
coulOlnb potenti:!.l barrier and get close enough so that nucle:.r forces produce the
necCilSary consolidating netion. T his problem is not present in nuclear fission be-
cause the neUlron docs not have lUI elcctric charge, and thlls can ap proach the
nucleus evcn if its kinetic encrgy is very small or practically ~ero. Since t he cou-
lomb barrier inefC3SCl> with atomic !lumber, nuclear fusion occu~ at reasonable
kinetic encrgies only for very light nuclei with low atomic number or nuclear charge.
We s hall noll' estimate the kinctie energy required to place two lIuclei of atom ic
numbers Z I and Z2 in contact. Let r in the clE!(!tnc potemial energy of two nuclei
(E'" = ZeZ:ze'/ '\1rfor) be equal to the sum of the lIuclear radii, or nbout 10- 14 Ill.
T heil \\e obt.'lin E,. - 2.4 X 1O- 14Z 1Z 2 J = 1.5 X 106Z I Z 2 eV = O.I5Z 1Z :'IIeV.
T his gives the height of the l>Olentilll barrier !md therefore the Illinimtlm~ initial
relative kinetic cnergy of the two nuclei lIecessary for fusion to occur. If the col-
liding p:lTticles do not have a kinetic energy C<lu.'l1 to or larger thnn E p , fusion
canIl0.t. occur. HOII'ev.er, at en{'rgie~ slightly lower than HI' t here is some probability
of fU Sion by p:netratlo~l of the coulomb barrier. T he average kinetic energy of a
system of I>:lrtlcles haVing a tem l>eraturCl T is of the order of kT, or nbout
8.6 X 1O -~ 1 ' eV,
where 'I' is in absolute degrees. Thus the energy of 1O~ eV corresponds to a tempera-
ture of about 10' "K, which is much higher than the temperatures believed to exist
at lhe center of the SUII. Even so, fusion is one of the Illost import81\l processes
 -
(8.1 '.7) Nutkar Jurian 365
364 Nlle/ror PNJCf!lIt.

occurring in the sun, Ilnd is its maill source of ClIergy. The fusion takes plMe A fusion reaction which has a large cross sccLioll and which liberates 11 great
among the relatively small numbe r of light nuclei which have energies weI! above amount of energy is Ihllt betwccn deuterium and tritium:
the average energy at the sun's temperature.
We conclude thal, if nuclear fusion of tl. lnrgc number of nuclei is to take plnce,
iH +: H - t ~He +n + 17.6 MeV. (8.32)
it is necessary for the !'Cacting nuclei to be at temperatures much higher than those Another pclISSible deutcrium fusion reaction, involving 'He, is
generated by CVCIl the most exocrgic chemical reaction. The extreme tcmpCr:l.ture
crentes n problem of containment of the reacting particles, since no know n matcri:t] ~H + ~ He -t :lIe + 1H + 18.3 MeV. (8.33)
can sustain such temperature. Also, at these temperatures, the nuclei nre stripped
of all their surrounding electrons (becausc of collisions) and the substancc con- Howe~er, since .tri ti\ll\\ and aBc are not sa rendily avnilnble, the fusion of two
sists of a neutral mixture of positively charged nuclei and negative electrons called d.euteT1 ulll nucleI or deuterons is of more practical importnncc. T his has the Mldi-
tlOlII\l advantage of using only one class
a l)/asma. C<Jntainment has been attempted by mcans of magnctic ficlds. Ablo,
of nuclei. The resulting products may be 10,---,_ _,-_ _-,
whcn the intensity of the magnetic fields is rapidly increased, the plasma is com-
different; two possibilities occur \\"ith
pressed adiabatically Bnd its temperature increases until fusion begins. Several
about the same probability:
ingenious devices have been built that perform these two functions of containment
and heMing. ~ He + II + 3.2 MeV
As we may sec by referring to Fig. 7- 6, energy is liberated in nuclear fusion of /'
light. nuclei (A < 20). When two llght nuclei coalesce into a heavier one, the bind- ~H + ~H E
ing energy of the product nucleus is greater than the sum of the binding energies of
the two lighter nuclei. and this result.'! in a liberation of energy. If the conditions
\.
fH + IH + 4.2 MeV
'.-
are appropriate, the energy liberated in fusion is cnough to excite other nuclei, and (8.34)
II. chain reaction n~~ ult$. The chn.in reaction becomes II. nuc:len.r explosion by a
mechanism similar to a chemical explosion, but in this case the eXI)IO$ion is due to T he cross sections for processes (8.32)
lIucle:u instead of electriClI1 forces. The chain reactiol\ may nlsa occur undcr con- and (8.3'1) arc shown in Fig. 8-20.
trolled conditions, nlthough no fully sntisfactory fusion reactor hn.s yet becn built.
The simplest fu sion ren.ction is the capture of a neutron by a proton (or hydrogen
nucleus) to form n deuteron:
IH +n -t iH + 2.226 MeV. (8.29)
The great ndvnntn.ge of this reaction is that there is no electrical potential barrier Fig. 8-20. Cross sections of the deuteron-
deuteron and deuteron-triton fusion re-
to be ovcrcomc. As will be seen in the next section, scientists assume that this actions as a (uncI.ion of deuteron energy.
fusion reaction played 1m important role in the early stnges of the evolution of the (Dnt~ frorn A. BIShol), Projeet Sherwood, IO~ c,

,
---''f,;L
10
---:',,
Hil
__--.J.1()l
\lIliverse. At present, however, this fusioll reaction is re[,\lively unimportant due Refldmg, l\lass.: Addison-Wc$ley, 1958]
De"teroo ene'lO. ke \'
to the lack of a suflicient number of free neutrons. Nevertheless, reaction (8.29)
oceurs when neutrons from a nuclear ren.ctor diffuse through a hydrogencous sub-
Althou.gh th~ energy released in a single fusion reaction is much less than that
stance, such as water or paraflin. relcn.sc:tt III.a slllglc ~ssion reaction, the energy I>cr uni t mass is lnrger (becausc
Another simple fusion reactioll is that between two protons. Since a diprotoll
deuterl~m 18 a vcry lIght fuel). For the deuterium-deuterium fusion reflction the
nucleus does not exist, the process is accompanied by the conversion of olle of the
energy I~ about ~ X IOI~ J [>or kilogram of fuel. This is more thall double the ~alue
protons into a ncutron at the expensc of the binding energy of the resulting deu-
f~r Urallt\Ull fiSSIOn. Due to the relative abund:lIlce of deuterium (nbout one deute-
teron, and the emission of a positron "nd a neutrino. That is,
rIum ~~om for abol." 7000 hydro~en atoms), and th~ relatively lOll" cost of extract ing
IH + lH -t i H + e+ +" + 1.35 MeV. (8.30) deutellulll . from ,:atcr (about 30 pe r gram), f>clentisls predict that- once COII-
trol.le<!-fuSlOli devICes become practical-the fusion process will provide an ahllost
A third important fusioll re(lction is that betl\"~n hydrogen and deutcrium, re- ulllllluted l!Ource of cnergy.
sulting in n tritium nucleus: Fusion reactions arc the source of the energy of the sun and the other slars
One of the Illost important fusion I>rocesses is the BttJle or carbon eyelt, which i~
IH + iH -t ~H + e+ +" + 4.6 MeV. (8.3 1)

36. Nuckor prQuutl (8.7 8.8)

equivulcnt to the fusion of four protons into a hc.liUlll nucleus. The cycle occurs
in the following sleps :

lH+ I~C --+ I~N

I'N-01gC+c++v
III + I~C --+ L;N
(8.35)
IH + I~N_ 1:0
I~O -0 I~N + e+ +"

lI-I + I f N ---+ 1:0 + ~ Hc.

Add ing a!lthc reactions and canceling common terms, we have

4 III _ : He + 2c+ + 2v + 26.7 MeV. (8.36) h is cslimntc<i that process (8.36) is occurring in tho sun at the rale of
5.64 X 1011 kg per second of hydrogen fusing into helium, with a rclen.se of
T he net. energy liberated in the process is 26.71'I'IcV, or about 6.6 X 10 14 J per kg 3.7 X lO ~s W. Of this, only about 1.8 X 1014 W falls on the earth, mostly in the
of lH cOllljumoo. Notc that the carbon atom is a sort of cataly.l:Cf, since it is re- fo rm of electromagnetic radiation; however, this is still IO ~ times greater than all
generated at. the end of the cycle. The time required for a carbon atom to go the industrial power genemtc<i on the earth.
through this cycle in the sun is about 6 X 1011 yeai'll. T he cycle is shown sehcmat.-
lcftlly in Fig. 8-21.
8.11 Th, flrigin 01 th e Ele IR"nt8

~I[c
We shall now consider the interesting and important qucstion of the origin of the
clements. Dy origin we mean the mec hanism by which the present composition of
the universe was achieved, assuming the existence of certain primeval mntter.
T he stalements we shall make are merely speculative. since there is only incom-
'II.; plete evidence avai lnble.
Fig. 8--2 1. The carbon cycle. One of the clues \\'e usc fo r our speculation is the relative abundancc in the
universe of the different chemical elements. as shown in Fig. 8-23, nnd the other is
their isotopic composition. As we can see from the figure, hydrogen is the most
Another fusion reaction in stars is lhe Critchfield or l)r%n-prolon cycle, which abundant., followed by helium. After the sudden d rop in lIbundance corresponding
consists of the followillg steps: to lithium, beryllium. and boron, the abundancc follows a regularly decreasing
trend. leveling off for Z > 35 or .4 > SO, but with sollie pronounced maxima,
~H + IT-I -t~ J-I +e++v especially for iron and neighboring nuclides. The clements stop at Z = 92, since
IH + iH -t ~ I-I e (8.37) the amount of existing nuclei with Z > 92 is essentially rero, although they have
been produced artificially in the laborntory up to Z = 103. As to isotopic COlll-
~ H e+ ~ He -> ; l-Ie + 21 1-1 . position, the lighter elements tire richer in those stable isotopes with lower neutron
Properly combined, these retlctions tllso yield Eq. (8.36). The period of the proton- content, while the heavier nuclei tire richer in isotopes with higher neutron content.
prolon cycle in the sun is about 3 X 10' yean!. The cycle is shown schematically Also, evell-A nuclei are more abundant than odd-A nuclei. Another interesting
in Fig. 8-22. feature is that no nuclei with A = 5 or 8 are found in nature.
As explained in the next S(!Ction, Wltrophysicists believe that the proton-proton T he relative abundnnee and isotopic composition h:l\'e been found to be the
cycle presently predominates over the cnrbon cycle in lhc sun and stars of similar same not only ill samples taken from various pnrts and de pths of the earth'!:! crust
structure, but that in many younger slars tho situAtion is the reverse and the but abo in samples taken from meteorites which have fallen on the earlh from
carbon cycle is more importnllt. I n older stll.r:s that have mueh higher tempera- outer space. This constant eOl1l]}Qsition suggest.!:! that, at least in our galaxy, the
tures, other types of fusion reactions arc also believed to take place. elements were all formed by RI)proximntcly the same process. The ~zero time~

A
 ..
368 (s.s
tn - I
, which is followed, in about 1O-!6 5, by the decay process
o
'" '" W
7. ''''
Fig. 8-23. Cosmic :lbund:mce of the elC'!n<'nli. [D:ltl\ from 1-1. UI'1'}' :lnd H. Brown,
Pll y,. Rt~. 88, 248 (1952)1
of t.he proccss is ('Stillllited lO h:wc OCClIl'red at. about. (8 2) X lOB years ngo.
This figurc II'IIS obtained by taking into account. sever,l\ IJ..Sll'O physienJ cOllsidern~
tiOIlS, such as the velocity of receding gal:\xie:s, and by analyzing the natural radio-
:Ietive chains.
l\ltmy theories h:lve bccu aclv:lIlced to explain this gencral composition of the
uni\'ersc, but no ~ingle theory is oompletely I'>.'ltisfaetory. The llIost acceptable
theory at this time (nttri butable to Fowler, lIoyle, Burbridge, and Greenstein,
among others) postulate.!! that the clements 111'0 synthesized in stars under varying
conditions. The sequence of cvents c:ontempiflted by this theory is tiS follows:
SUPl)Osc that initililly (i.e., nt ~lcro lime") there is a very large 11IILSS of gaseous
hydrogcn (with, perhaps, some free neutrons). Due to stntistic:tl fluctuations and
gravitntional interaction, some of thi" hydrogen llIay cOlldell!lC into clusters, or
lS ta rs, reaching a density of the o rder of 10 5 kg m- 3 . In the process of eondens..'ltion
there is a tr"LlIlsformaliOIl of gt".lvil:ltioll:tl potential encrgy into kinetic cnergy,
re<ulting in an increase (Jf temperature (I" about 10 7 1\) of the gas. At such
lel11l)CmtuI'CS the 1)I'OLOlI-protOIl cycle of Eq. (8.37) is IXls,'.ible. lIelium thus be-
gin~ to Uc formed. It i", pos.~iblc Ihal, as by~product reactions of the proton~
protOLl cycle, relatively small quantities of nuclei wilh higher atomic mass may
be formed. For eX:lLuple, ~ Li is produced by the process
~ lI e + ~lIe -- !Bc + 'Y,
H
S.S) The origin oj Iht, tlf-mtnl, 369
l'art of the lithium reverts back to helium through the reaction
~ Li + lH -t ; He + ~ He.
Other fusion reactions, such as (8.29), (8.31), and (8.33), may also take I)lace, but
in much less amount.
Since helium is more massive than hydrogen, the helium nuclei produced in the
proton~proton cycle are carried to the center (or core) of the star by gravitAtiollal
action. The density at the core may then become as high as 108 kg m- 3. The
resultant gain in kinetic energy of the helium nuclei at the corc incrcnses the core
temperature (up to values of 10 8 1\:). The surface temperature of a stAr in whose
interior A large quantit.y of helium nuclei has accumulated increases and its oolor
conSC<juently changes. The increase in temperature and density of helium nuclei
at the core increases the possibility for the production of :Be by the helium fusion
reaction
;He +~ H c - t :8e,
:ne -t hIc + :Hc.
H owever, duc to the relatively large helium concentration, it is possible for another
helium nucleus to be captured before this decay occurs, resulting in the reaction
:Be + ~He -+ ! ~e.
Alternativcly, the intermediAte products in the proton~protOI\ ChAiLl ~H and ~He
may be captured by the beryllium, forming LgB and I ~C, respectively, although
in much smaller amounts than ! le. Also many other less-probable reactions can
take place which result ill ot.her light. elements.
The chain of events just described explains how the gaps at A = 5 Ilnd 8 can
be bypassed. This mechanism also makes the scarcity of lithium, beryllium, and
boron understandable, as wcll as explaining the relatively great abundance of L~e.
By the same process of helium capture, the production of successively more mllSSive
nuclei such as !:O, i&Nc, Zlnd others is l)OSSiblc. The only limitation to helium
capture is the amount of energy required by the ~He nuclei to overcome t.he cou~
lomb repulsion of the heavier nucleus. Figure 8-24 is a schematic representation
of the series of events proposed by this theory of helium capture (or burning).
)-_--'-{ ':0)-_ --'-(::;-, e
Fig. 8-2-1. The helium buroing process.
 ..
370 Nuckar prOCUUI (8.8 PrOOIenu J7I

The thoory of the o rigin of the clements is Illueh more complex thnn our limited
With the production of heavier nuclei grent quantities of helium are used up
review can possi bly indicate, but. wc cannot explore thi.s matter in greater detail
nnd a further gravitational contrnclioll of the star should take place, leading to
here. What. we have said should be enough to make the student :\pprccinte the
core densities of the order of 10' kg rn- 3 (wi th a corresponding increase in the
idcM explored in this inteTCSting, challenging, :.tnd creative Mea of physics.
kinetic energy of the nuclei and fl core tcmpcrnt.uro which Ililproachcs 10 9 OK).
Under such conditions of very high density and extreme tcmpcmturc, other nuclear
rcnctions arc possible which muy I>roducc nuclei of higher mass number, up to the
iron group (about II = GO), but not heavier, due to the energy limilniions men-
tioned nbovc. Free neutrons mny be produced in some instances through (cr, II)
rellctions, such SlI ]. "HellOurce Letter NR-] on Nuclear Reactions, ~ T. Griffy, tim . J. l'h ll~. :n, 297 (!!l6i)
2. ~Thc DiSCQl"ery of Nuclear FiMlion," II. Graeber, .Im. J. Ph y. 32, 9 (1964)
I~C+ ~J[c -+ Ilo + II, 3. "A Study of the Discovery of Fi~ion," E. Sparbcrg, .Im. J. Phy . 32, 2 (1964)
~Kuclear Fission,~ R. Leachman, Sci . . Im., August 1965, Ill1.ge 49
I~O + ~He --+ rgNc + II, 4.
5. ~Thermonuclear He3ctions," G. Tho~n, .tm. J. Phy . 28. 221 (1900)
~ANe + ~I-lc -- H:'-.Ig + II. 6. ~Hccenl Delelopment~ in Controlled Fusion, A. Hishoj), Phym. Today, ;\[atch 1964,
H

page 19
These neutrons, together with some of the original (or primeval) neutrons which
h:lllc not decayoo into protons, IIrc IlIIai1:Lblc for extending the production of 7. ~T h~ ?rigin ~f the Elc.menUJ~ by W. A. Fowlcr and "The Structurc of Nuclci" by
V. II clsskopf 1Il Tile Scun/iftc lil/dellvor. New York: Rockefellcr Institute Prcoss, 196.5
nuclei to highcr mass Ilumbcrs- thnt is, nuclei beyond thc iron group-by neutron
capture rathcr than by the capture of charged I):lrticles. I n mllny instances ncu~ S. S/n;~/ureof Maller, W. Finkelnbutg. New York: ,\eademic PrC8ll, 1964, Chaptet Y,
Sections 9-]9
trotl capture TC.'lctions rcsul L in ,8--decay (as we have seen, evcry time a nucleus
acquires too many ncutrons, it decays by clectron emission). The resultant nu- 9 . I'rillcipi. of J!odeTII PhYlie., H. Leighton. Nc'" York : ;\lcGraw-lIil1, ]959, Chal)-
tOT<J ]6 and ]7
cleus has a higher atomic number after the ,8--decay and the chain can thus ado.
vllnce tOW:l.rd highcr Z-valucs. Of course, as time passes, lhe number of free 10. Nue/cor PhI/riel, 1. Kaplan. Heading, Zl lass.: Addison-Wesley, 1963
nculrons decreases. This then is an cxplttnntion for the fact that the hcu.vier elemcnt.s 10 the .I/omi;:: .""uclell." J. Cuninghame. AnlSteroam: Elscvier, 1964
I I. illJrodw:lio,\
arc relatively less abu ndant s.ince the production of the heavicr clements is almost 12. RadiooC/irU!I and I II JflUuremelll, W. :\Iann and S. Garfinkel. Princeton, KJ.:
entircly dependcllt Oil neutron Cfil)ture. Van Nostrand, ~Iomentum Books, 1966
Since the initial "firing-U I)~ of a star is based on a statistical fluclualioll, the 13 .. t Source Book in Phy,iu, W, Magie. Cambridge, ~Iass.: H:l.rVllrd Ulliversity Pross
sttll"l> in the universe cannot all be expected to follow the SlLme sCf]uence lit the (1963); pagc 6]3 (Becquerct)j page 6t7 (I'. and :\1. S. Curie)
same mte, fUld the slill"5 are prescntly in different stages of evolution. T he sun
itself is still mostly in the first stage of evolution; its composition is :.tssuilled to be
81.76% hydrogen , 18.li% helium, and O.Oi% for the rest of the elements. Stars
in which the Protoll-I)rolon cycle I)resclllly appears to be the dominanL process
are called maill .sequence 8lars. Those stars in which at. present it. appe:l.1"l> that the 8.1 The hair-life of 'XISr is 28 yeaN. activity ag:i.inn lhe time. (b) fo'ind the dis-
most imllOrtant process is helium-burning are called red uianls because of thei r
color. In nl[ln), stal"l> the three stages of Iiucleosynlhcsis proposed by th is theory
Determine: (a) the disinlegrntion constant
for !lOSr, (bl the sctivity of ] mg of 80S r
integrstion constant and the half-life of lhe
I!Smple. (e) IIO"' mauy rndiOl1ctive nuclei
are nssumed to be taking pbce simultancously, with hydrogen-burning occurring in curiel and as nuclei per second, (0) the WCTC pt('"scnl in the I!llmple at t _ 0 s?
at. the surface, he lium reactionll prevailing at. an intermediate (and ho~ter) !:\yer, time fot the ] mg to reduce to 250pg, 8.3 .\ m:uerbl i$ compo!!C(\ of two differ-
and heavy clcments being produced in the much hottcr core of the stM. Stars th:.tt (d) the activity :l.t this tater time. ent mdioActive sub.;s tan c~ having half-lives
have evolved in the IIny predicted by this tlll!{)ry are cnlled jir81-yelleralioll SIUT8. 8.2 A freshly prepared sample of a radio- equal to 2 hr~ und 20 min., rCl!pcctively.
I n some instances inst:.tbilities which arise during the evolution and :.tging of n active mater;:l.I, which decay" to II. stable Initialty thf'l"e i~ one mCi of the first sub-
star may rcsult in the ejection of ~ome of the material from its interior into inter- Iluclidc, h:\~ it", (lctivit)' mcasllrc every stance and 0) mCi of the !lCcond. ((I) U.'ing
stell:.tr space, where it mixes with uneondensed hydrogen and the dust of outer 20 8('{'onds. The following activity (in ~emilog(lrith!nic paper, plot, a~ fllnetions
space. Condens..'llion of some of this mixture at some later tillle rcsul18 in secolld- .IICi) is mCll!lllrcd st:l.rting at / - Os: 0.110; of time, the activity of each ~ lIb~tJ!.llce (lnd
(ulld later) ye1leralioll stnrs. I t is in these younger stars that the eMbon cycle, ]90 ; 90; 0.13; 20; 9.6; -1.5; 2.15; 1.00; 0.0.\8; also of the wholc llIateriul. (b) At what
0.23. (a) Plot the natural logarithm or the lime is the tOla] acth'ily one mei? (c) At
Eq. (8.35), plays nli iml>ortant role.

372 Nuckar pl"OUUU
what time is the activity of the short-lived
substance 1% of the long-lived substance?
8.4 The activity of a material is nlC1l.sured
every SO s and the following values (in
eounl.8 per minute) are found: 1167; 264;
Ill; 67; 48.3; 37.1; 30.0; 24.6; 20.9; 18.1;
15.7; 13.9; 12.3; 11 .1; \"1.84;8.85; 7.83; 7.02;
6.2ti; 5.00; 5.00. (a) Plot the logarithm of
the nctivity vcrsus timc. (b) Dctermine
how many radioactive subst:l.I1ces nre pres-
ent and compute the haH-life and disintc-
gmtion colllitnn~ of each. [lIi1It: First
subt ract the activity of the longest-Ii\'ed
substance by extending the tail of the curve
in a straight line back to ~ro time. Plot
the remaining activity and rep,eat the proc-
eM ulltil a straight line, eOTTcspondin g to
the shor tcst-lived substance, remains.]
8.5 Show that the average li/e, 1', of a
radiop,ctive substance is given by
I
T ... - - l'
No .Yo
I
tdN .. -
>.
8.6 Solve Example 8.2, 9.$'!uming that
initially there are No nuclei of the radio-
active substance. Consider particularly
th e cases in which No < gf>.. and No > flf)..
8.7 lleferring to Example 8.3, show that
the number of nuclei of m(l,lerisl C (a sbble
nuclide), fI<! f. function of time, is given by
\' NAO
lC"},1t - },A
X [},s(i - e-~A') - },A( I - e-~H')].
8.8 lleferring to Fig. 8-4, show that the
time a~ which the number of nuclei of "lIb-
st:Lnce B is maximum is equal to
8.9 A blecl [)i~ton ring with a ma.'l.~ of 25 g
is irradiated in p, nucle(l,r renetor until it~
.!!.ctivity is \"1.0 mCi (due to the nuclide 61IFe
which has a half-life of 3.90 X 10 s). Two
osys Inter the piston ring is installed in a
tcst engine. After a ten-day test run, the
..
crankcase oil is drained and studied for
:Lctivity due to .ro'Fe. In\'cstigation shows
an average activity of \"1.8 X IO~ disintcgra4
lions per second for a 200-cm 3 sample of
th e oil. Compute the m~ of iron worn off
the piston ring, given' that the crankcase
has 11. cSJl(l,city of 7.6 liters.
8.10 The nct ivity of carbon found in living
specimens is 0.007 pCi per kilogram, due to
the HC present. The charcoal taken from
the fire pit of an Indian campsite has an
acti\-ily of 0.00-18 pCi kg-I. The half-life of
HC is 5760 years. Calculate the yea r the
csmpsite was last used.
8. 11 Plot the logarithm of the disinlegrs-
lion oonstan~ \'eI"3Ull the energy for the a-
decays listed in Tsble 8 41. Show that the
points lie (l,pproximately along a straight
line, so that log}, .. af:. + b. Determine
(I nnd b for bt"!Jt fit.
8.12 Calculate the energy of the OI-parti-
cle released by IHl\"d when it deeayti to
HOee. Also calculate the recoil energy of
the daughter nucleus. The rcst masses
are 143.9100 IImu snd 139.005~ amu,
respectively.
8. 13 An clastic collision betwecn an 01-
Jlarticle and a nucleus of unknown mass
is observed in IL cloud chambcr. The 01-
particle is deflected 55' from il.8 original
direction, while the nucleus leaves a track
which makes sn angle of 35 with the in-
cident direction. What i~ the mMlS of the
nucleus?
8. 14 The range, R, of OI-particles in air
and the a-particle energies E are related
by theemJlirical relation R - 0.3183/2 m,
where E is in :\ leV. (a) For th ea-Jl(l,rticle
energics shown in Fig. 8-8, determine th e
range of the (I-particles emitted when 2L Lm
decays. (b) The (I-detay of 212PO is ob-
served in n cloud chamber, and four
ranges-I 1.2, 11.0, 9.57, ,~nd 8.51 em-
nre measured. Ctlicul!l.le the energies of
th ese OI-p(l,rticle. (See Fig. 8-9.)
8.15 The (I-decay spectrum from 226Ra
hfl<! a trilliet st ructure, with (I-particle
energies of 4.777, 4.593, and 4.342 MeV.
Assuming that the daughter nuclide 222Rn
iSllroduccd with a ground and two excited
slate, drnw th e energy-level diagram and
show the 1'-rsy emission ll580ciated with
the tr.!!.nsition.
8.16 Show th e possible modes of decay for
.0 1(, which has !I. res t mass of 39.96.10 nnllL.
Compute the energy available for ench
l>OMi ble proeesa.
8.17 Show from mass measurements th(l.t
'Cu may decay by {J+- and {J--cmission,
or electron capture. Experimentally, we
know that 6Cu has a half_life of 12.8 houl"3
with 39% {J-, 19% {J+, snd 42% EC.
Compute the energy availsble for each of
the three processes.
8. 18 (a) Show thst 713e decays by elec-
tron capture. 11.8 rest msss is 7.016929 amu.
(b) Compute the energy and the momentum
of the neutrino and the daughte r 7Li
nucleus.
8. 1\"1 Calculate the ms~imum energy for
the electron in the (J--decay of ' H.
8.20 When 140 decays by ,6+-cmission, the
daughter UN nuclide is almOllt always in
an excited state (>99%). From the experi-
mental dat.!!. which are given in Fig. 8-IO(b)
and from the fact that UN has a rest maS!!
of 14.003074 amu, calculate the mass of
14
0.
8.21 Plot the masses of isobars with
JI _ 40, 64, and 134 against Z. Sho\\'
the possible ehaillil of {J-decaY8 find the
most stable nuclides. Join the upper and
lower vfllues, starting from th e stable
nuelidcs, and note that the connecting
lines are parabolas. ~Ieasure the msss
scparation between the two lincs and show
that it is consistent with the odd-cven
con'Cl:tion term of Eq. (7. 11),
8 _ 34/1-3N MeV.
8.22 Plot the energy distribution or dce4
trons in {J-decay, fI<! gi\'cn by I~q. (8.21 ),
for ":0 - 1.2~ MeV. Compare with
Fig.8-II (b).
37J
8.23 Comillete the following nuclear re-
action equatiOIlli, substituting the correct
nuclide or psrticle wherever an X appcllrs:
(a) iiAI(n, (I) X; (b) Hp(1', n)X;
(c) nl'(d, p).\'"; (d) LijC(X,OI)~I3e;
(e) J~B (1', .\'")~Be; (0 Il~ l l1(n, "Y)X;
(g) HNi(p, n).\"; (h) ~?Co(n, X)~Co.
8.24 The mall! dc/tet of a nucleu~ is defined
asd .. /1 ~ .11, where.1 is the mass num-
ber and .II the nuclear mass in amu.
Expresa the Q-value for p-- and ,6+-decay
and the reaction M,(m;, rII,).I/" in terms
of the value of the mass defect tJ. for each
of the particlcs involved. IlIin!: See
Examples 8.4 and 8.5.]
8.25 A particle with mass ilL; is projected
with IL kineti c ene rgy t:~ (in the I ..... frnme of
reference) ag(l,inst a nucleus of mass M i
initially at rCl!t in the Iflboratory. Show
tllllt (a) the total kinetic energy of the sys-
tem in the C-frame is E~M j( M; + mil,
(b) the total energy a\'lIilable for the reac-
tion .1/,(m;, rII,).l/, is Q + E~.I/ J( M; + m;),
and (c) the threshold kinetic energy of rII,
in the L-frame of reference (when Q is
negative) is ~Q(.I/; + 11I;)/ ,lI,. Assume
that the particles efln be treated non-
relativistically,
8.26 For the photonllc1ellr resction
2~:'lg("Y, n) 23:\lg,
determine the threshold energy of the
photon. The rcst rnll5M!>J of the Jlarent find
Ilroduet nuclides are 23.98504 snd 22.!I9~12
amu, rcspecth-ely.
8.27 A certain accelerating machine can
p,ccelerate singly charged particles to sn
energy of 2 ;\leV find doubly chflrged
particles to 4l\leV. What reactions may
be observed when 12C i ~ bombflrded by
protons, deuterons, ILnd (I-pflrticles from
this machine?
8.28 When 7Li ill bombarded by O.iO-
MeV protons, two OI-llnrtic1es are produced,
each with 9.0 MeV kineti c energy. (a) Cal-
,
374
cul:J.tc the Q of the reac t ion. (b) Calculate
the difference between t he tot:l.! kinetic
energy of the a-p!lrti clC$ !l.nd lhe kinetic
ellergy of the initial proton in the IArllm('.
8.29 The rest mlUS of MAl i~ 26.98154 amu.
Find the mlUS of the product nuclei for the
followi ng reactiOlllj:
(a) 21:\1(11, 'Y)28,\i, Q - 7.722 "leV;
{b} 27 AI (p, a) 2 ~ "lg, Q - l.SD' :" eV;
Q _ 5A!)7 MeV;
(e) 27 AI (d, p)28,\I,
(d ) 27AI(d, a)2~" l g, Q - 6.693 "leV.
8.30 Sho,"' that th e Q of a nuclear reaction
.If ,{III;, ",,).11, ill given by
where K/ i ~ the kineti c energy of the inci-
dent particle and ,,,'I i~ the kin et ic energy
of t hose III/ p.'lrticles observed Ilt an angle
of 00 with respect to the direction of the
incident particle.
S.3 1 For lhe following reactionll, find lhe
thre!hold energy of the projectile in Ihe I,...
fmme, assuming the target nucleus ill at
rc~ t; (a) I~N (a, 1') 170; (b) I&O(n, (r) L3C.
S.32 A sample of natu ral silicon is born
barded by a 2. 0-~leV beam of deu terons.
(a) Write all the I~ible reactions in
which ei ther a l)rotOn or an a-particle is
the ejected Ilarticle. {b} In each case, find
the kinetic energy of the ejected particle
in t he C-frame and its maxi mum and min-
imum kineti c energy ill the C-frame.
8.33 IH relatively low (thermal) energies
the neutron capture CI'Q!lS section for many
substances is in\'er.;ely proportional to the
\'elocity of the neutro n. Th is i.s called the
I/ u law. 1101" should the plot of the loga-
rithm of the thermal-neutron cross section
against the kinetic energy of the bombard-
ing neutron allpear?
8.3) Given t hat the ca.plure cross seelioJl
of LOJAu for neutron ~ follows the I/v law
(sec Problem 8.33), and that its capture
cross section for thermal neutrons
(0.025 eV) is !Y.l b, find the absorption
cross section of 187,\ U for I.O-eV neu-
trons. What thickness of a gold foil will
absorb 20% of a benm of 1.O-eV neutrons?
S.35 A tantalum foil 0.02 cm thick whose
density is 1.66 X JO~ kg m - a is irradiued
for 2 hr in a beam of thermal neutrons of
fl u:l: 10 16 ~ m- 2 jJ- l . The nucleus 182'fa ,
with a half-life 01 II " dar~, is formed as a
rC:!lult of t he reaction LSI Ta(n,1')l82Ta.
lmmediatdy after irradiatioll, the foil hM
nu activity of 1.23 X t0 7 disintegrations
per ~eco nd peT cm 2. Filld (a) the ~\umber
of LUTo. \luclei formed, (b) the cross sec-
tion for the (n, "Y) reaction producing IUTa.
8.36 A borated-steel sheet "hil'h is used IU
a control rod in 0. nuclear reactor is 1.59 mm
th ick a nd contains 20/0 boron by weight.
The absorption cross sections of iron and
boro n for energetic neutrons aTe 2.5 b (l.nd
755 b, respectively. (a) Find the macro-
SCOllic absorption cross scctions of each of
t hese elements in the borated-steel sheet.
(b) What fraction of a neutron beam is
absorbed ill passing through this sheet!
(c) Calculate the macro~opic cross section
of Ihe sheet if the boron content is increased
to 3%. (The density of bo roll i~ 2.5 X 10 3
kg 1ll - 3, and that of steel is 1.9 X 10 3
kg 111 - 3.)
8.37 A beam of 3iO-keV neutrons ill di -
reete<l at 0. liheet of alumi num foil 0.1 mm
thi ck. Given that the capture cr0S8 scttion
of aluminum for neutron ~ of that energy is
3 mb, see Fig. 8- H (b), determ ine the frac-
tion of neutrons captured. The density of
III11minum is 2.70 X t03 kg m- 3.
8.38 Repeat Problem 8.37 for a bellm of
neutrons whose energy is about 45 keV.
Figure 8- 14 (b) shows a peak in the capture
<:rOSll section of about IS mb at 45 keY.
8.3!) The capture ero.se section of IOn for
therma l neu trons ill about 4000 b. 110\\'
thick 3. layer of LOB is required to ab-
sorb 99% of all incident bea.m of th ermal
neutrons? (Density of boron ; 2.5 X 10 3
kg m- a.)
8.40 Show t hat ' Li i~ stable to fission by
analYling all the possible ways in which
+
it might split (for e:l:ample, ' Li ...... d a,
cte.). Similarly show that &I.i and 5IIe
arc ullstable to fiss ion.
8.'11 III th e photofl!;;;ion of 235U in to gOJ(r,
H213a, and three neu trons, calculate, from
the mMS differences, the wtal cne rgy re-
le1Sed. Compare this energy with the
initial coulomb repulsion enerlO' of the
two charged fragments, assuming tha~ they
arc just touching when fissio n OCCUTl!.
8.42 Calculate th e energy required to
split 110 4He nucleus into: (a) 311 and p;
(b) 31le and n. E:l:plllin t he difference be-
tween these energies in terms of the prop-
erties of nuclear forces .
8.43 Show that the energy relelUed in the
fission of uranium (185 MeV per atom) is
equivalent to 8.3 X IOu J kg -I . At what
ra te should uranium fission so that I MW
of power i~ generated? How long would it
take for I kg of uranium to be used up,
gi,'en that it is continuously generating
I )'IW of )lOwer?
8044 It may be shown that spontaneous
fission will occur if Q:2.4 /0aZ~ ... 25A / Z 2
is lellll t han uni ty, where (12 and (13 are
coefficients in t he Weiszlicker formula,
Eq. (7.lZ ). Calculate this ratio for tUXe,
IUCe, 200Hg, 23~U, and 255Fm.
8.'1.5 Compute the excitation energy of
the nucleus produced when a neutron is
calltured by each of t he following nuclei:
232Th, 2UTh, 233U, 23 4 U, 238 pu, and
240l'u. Which of these nu clei would
we expect to be fissionable by thermal
neutrOIlS?
8.46 (a) What mUllt be th e a\'erage tem-
perat ure of a deuterium plasma in order
fer fusion to take place! [llint: We may
estimate this by calculating the coulomb
repulsion energy between deuterons when
they are within the range of the nuclear
375
force, ""' IO- IS m.! (b) Calculate the energy
relea.'I(!d in th e fusion of two deuterium
nuclei into an a-part icle.
8.47 What ellergy is releawd in th e fusion
process 3 411 e __ L2C? T hill process oceul"lJ
ill the secolld stage of nucleosynthcsis in
slal"3. Determine the power generated by
thi3 proees., in a star in which 5 X IO v kg
of 4He are fUlled in 12C per 8CC(Ind .
8.48 The nitroge n cycle i~ a fusio n process
sim ilar to th e carbon cycle give n in
Eq. (8.35). It stllrts with the capture of
a photon by a 14N nucleull. After ~ucces
si ..c reac tio ns, in "'hich the nuclides I~,
UN, I!JQ, 171<'. and 170 are in\'ol\'ed, the
14K nucleus is regenerated, with the re-
sultant flLsion of four proto ns into an a-
particle. (a) \Vri te the different steps of
the nitrogen cycle in detAil. (b) What is
the to tal energy rcleased in the ni trogen
cycle?
8.49 Show that, if t he energy produced
by the sun is to be accounted for, its mass
must decrease at the rate of 4.6 X 109
kgs - I How much t ime must pM8 for
the m!\Sll of the sun to decrellSe by 1%
(m!\Sll of th e 6UII _ 1.98 X 1030 kg)?
8.50 How long would it take for the length
of the year to increase by one flCco nd due to
th e loS!! of mass of t he lIun by radiation?
(See preceding problem.) Recall t hat the
square of the period of the motion of a
planet around the sun is inversely propor-
tional to the mass of the su n.
8.51 AS!!uming that the rate at which
hydrogen is fused in to helium in the sun
since its beginning has remained the same,
show tha~ the age of the sun must be of
the orde r of 2 X 10LOyears. The estimated
age of the sun, based on other calculations,
ili of the order of lOll yeaTl!.
 ..
9 9.1)
FUNDAMENTAL
PARTICLES
9.1 f nlroduction
9.2 Particle Genealogy
9.3 Particles and Anliparlicks
9.4 Pari ide I flslabilify
9.5 The Conservation Laws
9.6 Invariance. Symmetry, and Conservalion Laws
9.7 Resonances
9.8 Whal f s a Fundamental Particle?
1nlrooucfiOfi 377
9 .1 IlItrOf/uction
We shall conclude our discussion of the struel.ure of matter by briefly considering
the building blocks of which all matter is composed. These building blocks arc the
fundamental or elementary parliclu, to which we have referred on several occasions.
So far in this text we have encountered the following particles: proton, neutron,
electron, positron, and neutrino. T o this list we may add the photon, which is also
considered to be a fundamental particle. The first three particles seem to be the
only ones needed to explain the structure of aloms and nuclei. The positron ap-
pears to be unnecessary for tha~ purpose; its existence, howevcr, confirms the
validity of the relativistic and quantal idel\.'! when they are applied to thc rcallil
of fundamental particles (this requires It Illathematical analysis beyond the level
of this book). Apparently thc neutrino is required to 8Il.tisfy three basic Jaws:
the laws of conscrvation of energy, momentUIll, and angular momentum. And the
photon is the carrier of the clectromagnctic interaction betwccn charged particles.
T hat is, the electromagnetic interaction of LwO charges is described as an exchange
of photons (sec Scction 1.6).
i\ lay wc expect. more fundnmental particles to exist.? Rcasoning by analogy,
we may eX"!>cct that the strong interaction betwccn protollS and neutrons also
TC{Juires that there be a carricr particle, which we may call II. pion (after the name
:IT-meson originally given to it). And the gravitational interaction betwccn two
m:&SSCS should require thnt there be nnother carrier particle, which we call a grallifon .
Similarly, the weak inteT!\ction should be associated with a carrier particle, called
the W-I)arLicle. Indeed, l)ion8 have been observed in cosmic rays and lire produced
in large quantities in high4!nergy accclerat.ors, but no experimental evidence for
the gr:witon or the \V-particle has yet been found.
In the Inst 30 years many other particles (sometimes predicted, other times
UIlSUSpected) have been observed. Some of them seem to behave in rather strange
ways and no reason for their existence h[L.~ yet been found. 1\lore than 30 rclatively
stable particles (mean lives longer than 10- 10 s) have been identified. About 50
extremely short-lived particles (mean lives shorter than 10- 21 s), sometimes called
rtlOllaliCtl, have also been identified. These discoveries h!l.ve been made possible
by the constmction of very high-energy accelerators which produce particles with
an encrgy of several GeV, ns well as by the refinement in techniques of observing
particles. These techniques include eloud, bubblc, and spark chambers and photo-
graphic emulsions (ill all of which the charged particles leave visi ble tracks), dif-
fcrent kinds of dci.ectors-such as Geiger<\liiller, scintillation, and Cerellkov
counters- as well as rather sophisticated electronic circuitry. We shall not enter
here into a discussion of these experimental techniques; however, some of the
apparatus fo r partiele detcction is described in Appendix VIr.
Because the mathcmatical complexilie~ of the theory of fundamental 1)lI.rticlcs
go quite beyond the elementnry introduction to quantum mechanics given in
Chapter 2, our discussion of the subject in the following Pfl.gcs will be mostly quali-
tative and descriptive.
 po

378 FWldammlal parlitk. (9.2 9.3) PtlI'lidel and antiparticlel J79

TABLE 9-1 Fuudu ... enl a l Purlicl cs EI~tron 0-

.\111011
,
I I I I I'"I
I'hoton 1'000i lfOl)
Relit
R~.
Particle Symbol
m~

( in unit.!!
energy,
MeV
Charge
(in units
of e)
Spin
(in units
of h)
Anti-
particle I II
I I I I II I ! I I
of m..) 1000 1910 19"20 "30

I
1910
I ''''' I '''''I~
;:: -

,,
.l/ouhll bolon' I'ioro
Graviton (!)
Photon
0
0
0
0
0
0
2
1 , I'rotor,
~elltl'Ol1

:-;~utrino,.
:-;""lriM~

Lepta." (fermions)
Neutrino , 0 0 0 t , Fig. 9-1. Time table for the eXllerirnenlal discovery of Ihe fundamenlal]>articles. Some
Electron 0- 1 0.51t - 1 t ,+ particles were Ilredicl.ed on theoretical grounds prior to their experimental observation,
i\I uon ,- 206.8 105.7 - 1 I ,+ and others were observed unexpcdedly. (Adapted from C. S"'artz, Tht "'lIndamtnlal
Parlie/a, Addison-Wesley, 1965)
.1tUOM (bol!ons)
Pion .+ 273.9 140 +l 0 -
Kaon
.'K+ 264.2
966.7 .,.
135 0
+1
0
0
.'K- interactions; i.e., strong, eleetrolllagnetic, we:l.k, and gravitational. Leptons are
1!Ot scnsitive to strong intcractions, photol18 nrc rclatcd to t.he clectromagnctic
interaction, and grnvitolls to the grnvitational interaction.
K' 974.6 498 0 0 K'
lI- ffic:son 1074 '49 0 0 One of the mnny puzzling llnd ullwlved questions regarding fundnmcntal par-

Baryon' (fcr mions)

" " ticles is that the musscs of the particles do not seem to sho\\' nlly kind of regularity.
On the other hand, the particles 11re eithcr uncharged or have charges e, n fnet
Nucleons "'hieh must be closely relnted to the law of conserv'\tion of charge. Similarly, all
proion p+ 1836.2 938.3 +1 I p-
fermions have spin ;, c.xcept Q~, which seems to have a spin of t, and all bosons
I
neutron
"' 1838.7 939.6 0
"
.'
have zcro (mesons) or integral (photon) spin. :\1081. of the particles nlso have n
H Yllcronll
X' magnetic dipole moment.
lambda 2184 1116 0 I
sigma ~+ 2327 11 89 +1 I !- The spin of the photoll is inferred from the fnct t hnt all radiative transitions
~, involving the emission or absorption of photons by particles, nuclei, atoms, or
2:0 2333 1192 0 I
l - 2342 1197 - 1 t !+ molecules are strictly forbidden if both initial and final Slates h1Lve zero total
,; ::,:0 2573 1315 0 I ;;:0 !Lngular momentum. This shows that the photon caTTies some intrinsic angular
;::- 2585 1321 - 1 I ?:+ momentum, or spin. A more detailed analysis, which we omit, indicates that the
omega 0- 32i6 1674 -1 t n+ spin of the photon is I because the photon is associated with a vector field ; i.e.,
the electromagnetic field. Since the rest mass of the [>h010I1 is zero, it can be sho\\'1\
that. the photon spin can be either parallel (III,,,,. + 1) or llntiparalle\ (III. = - I),
0.2 '-nrilclp G"nf'nluy" but never perpendicular (111. = 0) to the photon's momentum. The first case
corresponds to left-handed and the second to righ~handed circularly polarized
Table 9--1 presents nEst of known (ci rca 19(17) particles (excluding the resonances),
radintion. This result is equivalent to the slnlement thnt the electromagnetic ficld
and also gives 80me of their properties. Figure 9-1 shows n time table for discovery
of a plane wave is perpendicular to the direction of propagation.
of these particles. The three basic quantities used to identify the particles are
mass, cllll.rge, aud sl>in; some other identifying properties will be given Inter.
!J "l 'urlid#!. unfl Antlpflrllcl,'"
According to their masses and the dominant interaction, the fundamental particles
are grouped into four fllmilies: (a) massless bO"01!8, (b) lepto/!s, or light. particles, For each particle, there is an associated al!/iparlic/e. T he anlil>:lrticles are listed
(c) me"OI/", or intermediate mass particles, and (d) baryons, or heavy particles. in the last column of Table 9- 1. An antil>arlicle is designated by the same symbol
(T he names boscr. Ilnd jermi01L added to those particles in T able 9-1 will be ex- as the particle, but with a bar over it. (Sometimes, for Ijimplicity, the bar is omit-
plained in Chapler 13, bllt. we may stnte in advnnce that fermions obey the exclu- ted.) Antiparticles have the IID.me mass and spin as the particles but opposite elec-
sion principle nnd bosons do not.) Baryons and mesons are subject to all fou r tromagnetic propert ies, such as charge and magnetic moment. (other properties, to


(9.3 9.3) Parlid~6 and Anliparlidu 381
380 Fundammlal par/ida
have p08ilive he/icily, eqlllli 10 + 1. This properly was found by means of un
!'~rtidell
,, AntiJlilrtidtd
analysis of the decay of pions and muons and also from p-decay (see Section 9.4).
,, For other particles of sl>in 1 which have nOI1l:ero rest mass (such as electrons), both
,
,,,
particle and anti particle lIlay have either positive or negative helici!.y, indis-
criminately; that is, ", = I.
,,
"'JO ,
,,, ~+ !O
,
,,, ~
-.
....1!- ....!.:...
~
,, -"- Fig. 9-3. The ueutrino and anti-
;:: , neutrino have oppositc helicitie!l. Neutrillo, . ,\Iltineulrino, ;

f~
,, ;\"eg:ali,.., hclie;ly Poo!Iiti'e hcolicily

~ other. Thei r total energy, including thei r rest energy, reappears in the form of
L,
,,
,,
,,
,,
.L
-'- ,,
o _ ,_ ..... + .....:.. ....L.
F ig. 9-2. Particles and antiparticles arranged according to their rest energy and charge.
be mentioned later 011, arc also opposite). Four particles-the phot0.n, the gravitol~J
and the 'lr 0 and ..,0 mesons-are their own antiparticles. The. Clusten~ of ~lIb.
particles is a re<luircmcnt of relativity snd quantum ~lechal\lcs. Anllpartlcles
were predicted by Dirac before they were observed expenmentally. In :rom~ cases,
the anti l)artic\cs have not yet been identified .experimental.ly, b.ut their eXistence
is assumed theo retically. I n Fig. G-2 the particles and antL]lartLcics are arr~ngcd
in a more symmetric way. The first antiparticle to be observed wa.'1 the posltr~m.
The American physicist Carl Anderson observed it in 1933, when he ,,:as an..n!yzm g
cosmic ray!.! with a cloud chamber. Antiprotons were first observed m 19,):) by :l.
group at the University of California; antineutrons were observed s~ort1~ a~ter\~'ard.
In the case of the neutrino, there is an important property whIch dlstlllg~lIshes
particle and antiparticle, and which is. a OOllscquence o.f the fact th~t theI r rest
mass is zero (and also because of parity nonconscrvatlOnj sec Sectlo.n 9.6). A
neutrino ulways has its spin pointing in a direction o ppos~te to ~hat of lts momen-
tum (which is ill the direction of motion), while for an o.ntmellt.nno.the I?Olllentum
and the spin are in the same direction (Fig. 9-3). A neut~no IS. S&.l~ to .have
flegalive helicily (designated as 04) equal to -1, and an antmeutnno IS SAId to
A particle and its anti l)article may combine, disappearing or aIlIlIM/alin!! each
other pnrticles. In the l)rOCeSS several conservation lnws must be !W.tisficd. For
exam ple, the electron e- and its antiparticle, the positron e+, may nnnihilate,
cillitting I)hotons, a process called elec/rOIi IJair alwihi/alion. If their spins are
opposite and their relative orbital angula r momentum is zero, the process is
(9. 1)
The reason that two photons fi re emitted is for energy nnd momentum conserva-
tion. If the electron and positron are at rest in the laboratory (which then coin-
cides with the C-frame), the total encrgy aVllilable is 2m..c2 = 1.022l\[eV and the
total momentum is zero. If II. photon of energy B., = 2m..c2 were emitted, it would
carry a momentum p, = E',/ c = 2m,.c and the principle of conservation of mo-
mentum would be violated, since the initial momentum is zero. To conserve energy
and momentum, two equal photons must be emitted in opposite directions. Thus
each I)hoton must have an energy equal to 1II..c 2 = O.5 1! ~leV. Photons of this
energy arc observed when I>ositrons from a ,6+-mdionctive nucleus p:LS8 through
matter. Angular momentum must also be conserved lind, if the electron and posi-
tron have their spins in opposite d irections, the photons must lilso have their
spins in oPI)()site directions, which requires thllt the photons have the same cir-
cular pola ri~fit ion (or must be 1>oIarized in pert>cndicular di rections). When either
the electron or the positron (or both) fire not at rest in the labonllory, the calcu-
lation can be curried out using the laws of oonservlltion of energy lind momentum
to obtain Ihe energy and momentum of the photons as measured in the laboratory.
Kote lhnt in Eq. (9. 1) charge is also conserved.
Prolon-antiproton annihilution is a more COIll I)lex process, involving the pro-
duction of several particles, most of them pions. One such annihilation (which
took place in !I bubble chamber) is shown in Fig. 9- 1, correspollding to the process
(9.2)

J82 F undamtnllli parlit.kf (9.3 9.3) I'arlick! IJnd anliptVlick, JaJ

duce<l, the photon must have nn energy equal to at least 2mei=2 = 1.022 MeV.
Tn o~dc r for energy and momcntum to be conscrvcJ in Eq. (1l.3), the process must
occur ileaI'II nucleus, which, ItS 11 result of its electromagnetic Cou l>ling with the
systelll, will take up the energy and momclltllln required for the conservation of
bo th qUlllllitics. For this rClUlOn elcctron iXlir production is more inteI\SC in mate-
rials which h:I\'c high atomic numbers (such ns lcad), since these materials provide
a strongcr electromagnetic coupling with the electron.J>ositron pair. Electron pair
l)rOOuetion is one of the main processes which accoullt for the absorption of high
energy photons by various materials. (At low cllergy the photoelectric effect. is
t he more important proccss, and at cncrgies betwccn 0. 1 )' JcV and I "lcV it is thc
Compton elTect. Sec Section \.9 :l.ILd Fig. 1- 19.)
Similarly, a protonantiproton I>air may be produced in a high-encrgy proton.
proton collision according to the scheme

(9.4)

(T his is not the only procCS!l that. may take place in 11. proton-prolan collision.)

._---........
, ..

Fig. 9-4. Proton-antiproton annihilation. ( Photograph courtesy of Brookhaven National

Laboratory)

T he incoming antiproton annihilates with one of the protons in the gas of the
chamber. If charge is to be conserved, t he number of positive and negative pions
must be the same. The number of w-.mesons produced is difficult to ascertain,
since they do not leave allY track in the chamber. The tolal number of pnrticlcs
produced depends on the energy avaii:l.blc.
C<lnvcrsely, a particle and its antil)articic may be produced simultaneously,
Figure 9-5 illustratcs the production of an clcctron-pooitron pair by a photon
ente ring 11 cloud chamber from the left; that is,
(0.3)

The track of the photon is not visible. Obviously, for an electroll pai r to be pro- Fig. 9-5. Electron-positron pair production. (I'hologra])h courtesy of Brookhaven
National Laboratory)
 ..
P(lr(ic/u (llid (llIliparlicitl 385
'84 Fundumtn!l,I/ porliclt' (9.3 9.3)

This process WtlS used by the Universi!y of California groul> in their expcrimcnta EXAMPLE 9.2. The antiproton eXIICriment.
leading to the discovery of lhe antiproton (see Example 9.2). In order for process Solu lion : Perhaps one of the mos t interesting UIICrimenls in t he phy!!ics of fundamental
(9.4) to occur, the threshold kinetic energy of the incoming I>rolon (if the ta rget partic\cs ill the experiment that led to the discovery of the antiproton. The purpose of
proton is at rest) has to be at least 5.64 GeV (see Example 9.3 for the calcu lntion the experiment Wll.S to detcct particles having a charge - t and a mass mp. Proton!!, ac-
of thi.!! value). cekrated up to 6. 2 GeV by the Uni\'efllity of Camorllia oovatron, hit a suitable target
Our galaxy seems to be composed mninly of particles (rather than a uniform ,,hich produced several react ions involving K'ij,7's, and p.'s, as "'ell &!I80me P- pJl.rtie1es.
mixture of particles nnd anti llarticles) and this makes it stable against annihila- A deHecting magnet .Ill selected only
tion. But nothing precludes the possibi lity thnt other galaxies may be composed negative particles, which were allo"'ed to 6.2-GeV proton:!
paM th rough an opening in the shielding from lJevatron
primarily of antillarticlcs, although no I>ositive evidence exists to support this
(Fig. 9-6). The S's in Fig. 9-6 arc scintilla-
assumption. In any CtISC it is inlcnl$ting to speculate on what would happen if Il tion detectors and the C's are Ccrenkov
galaxy and an Ilntigaiaxy were to collide. Astrophysicists have advanced the ideo. detectol'3. These instruments are flO made
that some of the cxplosions observed in distant galaxies may be due to a cata- that they are sensiti ve only tu particles in
clysmic matter-antimatter annihilation. a certain energy range (see Appendix VII ).
Between SI and S2 there was placed Jl.
EXAIHPUi 9.1. J)i$culISion of pMitronil4m, which is a system co mposed of an electron second deflecting magnet .\12, which acted
and fI. positron rcvolving About t hcir center of ms.ss, similar to the electron-proton ~yste m as fI. momentum selector, 8ince the radius
of hydrogcn. of the path \\'as fixed by the position of the
detectors, and unly particles with mo- 12 m
5<>1"' ;01.' Whcn Jl. Jlositron and an electron come close to caeh other, they may form a mentum p - tCBr were properly deflected
stable system whollC stationary states Jl.re eJl.lculated in the same manner lI.S the hydrogcn toward S2. Because it offered certain
stationary states diseussed ill Section 3.2. Recalling Eq. (3.7), we note that, ill the case eXIICrimelltal advantages, the magnetic
of positronium, the two particles have the same mass; that is, 111" - M, alld therefore fie ld was chosen to correspond to a mo-
the corresponding l1 ydberg conStant i~ Rt _ tR. When we introduce this \'alue ill mentum p _ 1.19 GeVjc, "'hich is slightly
Eq. (3.5) with Z - I , the BlationJl.ry energy levels of posilronium are given by leS!! than the momentum at which most
antiprotons should have been produced
, R.h 6.8 (1.75GeVjc).
b. - - - - - - 2eV.
2n2 n

The actual cnergy levcls arc gh'en by a more complex eXllre;;iiion, due to the relativistic
correct.ions which must 00 in t roduced. Because of thc possibility of pJl.ir annihiltr.tion,
accordmg to Eq. (9.1 ), llOI! itronium has a transient life. If the fJOSLt ron-clcctron Imir
moves \\'ith zcro orbital angular momentum (as in the Is ground state) and their spins
arc antiparallel (singlet ~ tate 'S), thcy cventually annihilate into two photons, either
circularly p.olarized in the same &Cllse or linearly polarized in peqICndieular planes, 113
previously ex plained. The half-life of the single state is 1.2 X IO- Io a. If thcir SpillS
are parallel (triplH state, 3S), then eonscrvlllion of angulJl.r momentum lI.S well as certain
Jl.dditiona[ selection rules rclated to the symmetry of the system forbid the decay into two
photons. Thus the positron-clectron pllir annihilate into three photons. T he energies of
the photons in each case must add up to 1.022 MeV, which is the total restcnergy of the
two Jl.nnihilJl.ting ptlfticlc~. The half-life of the triple~ stJl.te is 1.4 X 10- 7 s. The existence
of l>OlIitronium was confirmed in to;'il by :\Itlftin Deutsch. When a beam of l.ositrons
moves through Jl. gill!, a ccrtain number of the positrons form positronium atoms befure
anllihilation. The ratio of p\'obabi1itie~ (or forming singlet or tnl,let positl'onium ii; I to a.
Because of the mIlch longer life of trip\('t pusitl'onium, it can cntcr intu chemical reaction
with the atoms or moleculeS uf Lhl! glllj. In thi~ way posilronium halid(>~ havc 1lC'!:11 ob-
served. The~e "colllpou1\ds~ ~ holten the life uf the Jlositronium beC1!.1lS(! the positron may
annihilate with another electron of Ihe atom or mulcculc which hill! oJlposite spin. Active
rescarth is 110W being dOlle on the ~chcmistry" of posilronium.
'-ig. 9-6. EXIICrimental arrangement for
observation of the antiproton.
:\Iany negatively charged particles (K -,:rr-, p.-) and a few antiproton!! ( i~",1IS csti-
mated that the proportion ",lIS 40,000 other particle!! to one antiproton) p$SCd through
the magnet .112. To identify the antiprotons, it was nccessary to determine the velodty
of the particles. The velocity of an antiproton hJl.vin g a momentum of 1.19 GeVjc is
0.7&, ",hile the velocity of a pion of the same momenlum ill 0.99c. Thc seintill:l.tion
deteeturs St and S2 ",cre placed 12m apa rt; the time~ re(luired for Jl.n antiproton and a
pion with these momenta to go from Silo S2 were 5. 1 X 10- 8 9 and 4.0 X 1O-8 s,
respectl\'ely. T hus 81 Jl.nd S2 were placed;n delayed coincidence, so that they \\'ould give
a signal only if SI and S2 delivered ]lulses separated by 1> time interval of 5.1 X 10- 8 s.
lIence the observation of such delayed coincidcllces could be considered an indiclilioll of
lhe passage of an Jl.ntiproton. Howeve r, th e meson bnckgrouud was so heavy that addi-
tiona l precautions were required to eliminate accidental coincidences due to the pnssagc
of two different pions through 8. and S2 wilh a dela}' of 5.1 X 10- 8 8. Ccrenkuv dctector
CI was made sensitive only to particles wilh velocity greater than O.SOc Jl.nd C2 was made
BCllsitive ollly to particles with vclocity ootwccn O.7.x 11.11(1 0.7&. Thc antiprotons, by the
lime they arrived at the Cerenkov de\(.'ctors, had been 510w(>d down to Jl. velocity of about
 po

386 (9.4 9.4) ParlieU! irulabilily 387

TABLE ~2 Particle Decay Modes

0.7&. Thus C, WII.!! insensitive to anlil)rotollS but 1IC1lsitive to mC!lOlIij, and the revcr!!C
was trun for C2. T herefore, to prevent 8pUriOWI counts, the detector C1 1I'a.s connected in
ant icoincidence Ilnd C2 in coincidence with the ~ign81s from 8 1 and 82. That is, the Part;eJc Uclative nlllf.lift, ,.
Detay mode
experimenters knew that all antiproton had passed through the system onty when (a) 8, probability, %
aud 82 registered pulses delayed 6.1 X 10- 8 8, (b) C, did not register II. pulse, and (0) C2 !'hown Stllblc
rcgiswred II pulse. As 8n additional check, the magnetic fie ld of M2 was varied, and pulses
were received only when the value of the field corresponded to the preselected lillie of Nculrillo Stable
!light for Ilntiprotons. The expcrimcnt-pt'T[ormcd by Chamberlain, Segr6, Wiegand, and
Electron SlIlblc
Muon I' - ..... e-+ r +'
Ypsilantis in 195&-lI'lI.'I highly sue<:c!JSful, and confirmed the ex istence of the antiproton.
Pion 1.80 X IO - B

!J.4 Jnrticle In,,t,,,Jility

6 X 10- 11
The creation nnd annihilation processes discussed in the preceding section, as well
Ill! the process of P-declly discussed in &!etion 8.4, are manifestations of a more Kaon K+ ..... ,,++ r 63
general property of the fundamental Jlarticles: their instability. 111 other words,
(Iivell fh e proper cOlldiliolls, lilefwzdamelllaJ. particles call Ira/1sform bzlo olher particles
........ ++,.0
_ 2,.+ +,.-
_ r n+e++ r
..."
'.8
8.56 X IO - e

as It rC3ull of Ihcir ilzlcracliOI!. We shall soon clarify what we mean when we say
the propcr conditions. Particles which arc unstable undergo spolllaneous decay,
_ r n+ ,,++ r
_ ... ~+ 2rQ ..,
SA

".
with a well-defined half-lifc. T ablc!)-2 shows the decay modes and half-lives of KO ..... r.t.+cl'+r
unstable particles. I n cases in whieh Illore than onc decay modc is possible, the - ,. ~+ II" +. 4 X 10- 1
relative probability of each mode is !11M given. In SOme dec:\ys antineutrinos arc _"'++'0"-+ ,.0 6.3
iudicatcd; this is done in accordance with a conservation law (that of leptons) __ 3'0" 11.3
which will be discussed in Section 9.5. NOle that only four particles (and their
1---""- - -
antil>articles) arc stable ag(linst 6polltanoous decay: the photon, the lIeutrino, the "15
6.0 X to -II

electron, filld the proton. Of all the unstable particles, the one having the longest ~ O ""''Y +'Y 33
half-life is the neutron. This may expbin why matter is composed of electrons, ........0+.,+., 20
protons, and neutrons. ~ ote that mC:i!Ons h!lve a hnlf-life of the order of 10- 8 s ..... 3'0"0 20
(with the exception of the 7r 0 and '10), while the baryon half-lives are of the order ..... '0"++ ... -+ ...0 22
of 10- 10 8. ..... ,.++,.-+'l' 5
One condition necessary for sl)QlllanCQllS decay- a condition imposed by energy Prowli Stable
conservation- is that the rest ml\SS of the p..'lTCnt particle be larger than the sum 7.0XI02
Neutron
of the rest IIlflSSCS of the daugh ter panicles. In addition to energy, momentulll
Lambda ,\O_I'~ + ... - 66
as well as angular momentum arc sUPl>OSCdly oonserved. We usc this assumption 1.16 X 10- 10
uo + '0"0
as a guiding principle when we analyze the decays of fundalllenlal particles.
The negative muon was the first unstable particle observed (BOO Fig. !)-I). It Sigmll ~+
--0

..... p ... + ,.o

" 5.6 X 10- 11
was discovered in cosmic mys in 1937. The decay of a muon nlwnys resul~ in the ..... ,,0 + '0"+
nppcarance of nn electron. These electrons have a continuou.s spectrum of energy, <7 X 1O-1~
similar to that found in .B-dccay ( Fig. 8~1 1 ), with a maximum kine tic energy of Z- __ ~ +7- I . IXI~I O
about S3 ). feV. From these two fncts we deduce that muon decay cannot be a
two-body process, and that at lea.~t two neutral particles must be I)roduced in Xi :;;:0-0,..0 + ...0 -----t------------1--:,C
.oCXCC,OoC_"".--
addition to the etedron. Since the maximum energy of the clectron is much larger ;::-_ Ao + ... - 1.2 X lQ- I(\

than its rest. energy (0 ..1 )'leV), the maximum momentum of the electron is
O- ..... ,..o+ K-
-+-----+----
50
7'rnn = Emu/c = 53 ;\ leVIe. ..... ::;0+:1'- _--L_~~L--
50 _____

This maximum momentum occurs when the two other particles are both emitted To obtain the decay of llntiJl8rtid~, change all [lll.rticle! into ilntipllrticiCII on both
in the opposite direction to that of the electron, and both particles must carry a sides of the equations.
 -
388 Funda~nl(ll p<Ir{u;k~ (9.4 9.4) Parlick in,/(Ibi/ily 389

a neutrino is emitted ill the opposite direction. Since the nlOmentum of a muon
with the above kinetic energy is 29.5 l\leV Ie, this must also be the momentum of
the neutrino. The neutrino cnergy is then 29.5 i\ leV. Thus the total energy re-
leased in pion dccay is 105.7l\ leV + 4.1 MeV + 29.5 l\leV = 130.3 MeV, which
again approximately agrees with the rest energy of the pion, 140 l\leV, We may
thus assume that the decay scheme of the pion is as indicated in Table 9-2. From
the decay 11"+ ->,u.+ + v, we conclude that the spi n of the pion is eithcr 0 or l.
From an analysis of other processes involving pions, we conclude that the spin
is 0, Figure 9-7 shows the decay (i n !l bubble chnmber) of II. pion into a muon,
followed by the subsequent. decay of the muon into an electron. The aeeomp..'lny-
ing neutrinos do not. leave any trtlck. Observation of these double events is very
common.
Similarly, fig. G-S shows the decay of n knOll into three I)ions in a photographic
cmulsion. Analysis of lhe momenta of the three I)ions shows that no further neu-
tral p:utieles arc cmit.ted in the process; this is consisient with the laws of conser-
vlltion of momentum and energy. On the other hand, Fig. G-O shows thc decay of

Fig. 9-7. D~ay of a r - meson followed by the de<:ay of the muon. (Photograph courtesy
Brookhaven National Laboratory)
...
1;.
f:
t ..
I'
',

.
.
. '

.
'

.. '
;. ',.
~

-'i
f

total momentum of 53 ~ l eV Ie.

If the particles are Il Cutri llOS, thcir total energy
is then 53 i\lcV. Thus the total energy rdc!\SC<l in muon decay is about 106 :'IleV,
.
- ~~~1~
!" ' .~
(
.- '- ..I

__ ~~~
, ,..
I
'.

which is practically the rcst energy of the muon (Table 9-1). The s pin of the i . "'mCllOn

muon h fL'l bcclllllCasurod independently and found to be;; thus the Jaw of conser-
vation of angular momentum is another factor that would forbid the decay of a
I .
.1 .
'1 '. , "'"
muon into an electron and a neutrino, each having spin t. H oweve r, this Jaw does
allow for II muon decaying into an electron and two neutrinos. Therefore we may
'j '
.. _."
safely assume that the decay of IL negative muon can be represented by the decay t
I, ._
;..-
-.' .
.,
mode given in T able 9- 2. ~

T he next l)lUtidc to be ob8crved was the pion. It was first discovcrcd in 10W in I
p 0:
special photogflll)hic cmulsions (see Appendix VII) cxposed to cosmic rays, and J .\ .- '.
shortly afterward artificially produced (by protons accelerated in the synchrotron
at Berkeley). The existence of this particle had been prcdicted in 1035 by the
,
/
J apancsc physicist Hidcki Yuknwa to explain the short rangc of nudenr forces I
(see Section 0.8). The muons rcsulting from pion decay consistently have n fixed
kinetic cnergy of nbout 4.1 :\IeV, which indicates lhat pion decny is a two-body Fig. 9-8. I\meson d~l1y into three pions (the ,.mode). (Photograph courtesy of
problem. Therefore we may assume that in pion decay, in addition to the muon, Brookhaven National Labornt.ory)
 /
390 Pundllffltn/(,j fXIrlidt~ (9.4 9.4) Par/leu illl/abilily 391

I
I
I,.
I
I
,.
I

I
I
I
I
I
/1"
I
.' I
I
I

I
I
I
I
I

Fig. 9-9. Kmcson decay into two pions (t he 8-modc). (Photograph courte.~y of Brook- ,.' z~

haven National Laboratory)

ji -
a knon into a charged nnd a Ilcutrnl pIon. Figure !}-lO shows n more complcx
process, in which there is an initial proton-antiproton annihilation, giving rise to
a series of p.,\flicles which undergo subsequent decays. T he whole p~ can be
expressed by
fig. 9-10. Events triggered by Il proton-sntiproton annihilation. (I'hotogrll])h courtesy
of Brookh.iven Nationsl Lsboralory)

('.5)
]~Ot example, in a proton-proton collision, the following l)rocesscs may occur :

Each of the processes hns been carefully checked by means of the laws of conserva-
tion of energy and momentum. Such:\ check enables us to identify the ncu tml
par1icles which do not lc:tvc nny track.
The instability of a given particle is nl!'iO tli~pb.yed by lhe fact that, in a high-
energy collision bel ween tll"O p:\rticlcs, several new p:lrticlcs may be ]>roduecd.
(9.6)
Note that in eaeh case a pion is l>Toduccd. T he prolan-proton collision is the proc-
ess by which pions :Ire produced profusely in the laboratory. If oue of the pro-
tons is at rcst in the lnbomtoty, the th reshold of energy of the othcr proton is

....
 po

392 FU/Idamtllial parlidt, (9.4 9.4) Purlieu ins/ability 393

"
"

,
,, , ..'
."
. , p'

,, ,
,,
,
~, f 1,,0)
,, ,,, , "
,,
"",
- . ~,~.;---:,:.--

Fig. 9-1 1. Events triggered by a K-p eollision. (Phowgraph courtesy of Brookhaven Fig. 9-12. E"cnts triggered by fl cosmic-ray I)rotan colliding with a proton in the
national Laboratory) atmosphere.

about 300 MeV (see Example 9.3). At higher energies, other particlcs, such as n C:\I\ no longer be oonsidercd lIS billiard balls, which is a useful app roximation at
proton-antiproton pair, may result low energies.
Figure !}- II illustrates n more complex process by which a I{- and a p+ collide, Many of the processes involving fundamcntnl particles have been observed in
resulting in severnl particles which sufTer subsequent. decay. T he whole obscrvcd cwmic rays; that is, the flux of particles (mosUy protons) falling on the earth as a
process can be described by result. of nuclear processes occurring in the sun and other parts of the universe.
J{ - + p+ -.. ::- + 1\0 + 1r+ Cosmic-ray I>articles trigger a ch:lin of reactions when they interact. with nuclei
in the upper atmosphere. One such reaction is shown in Fig. 9- 12. Such a process
L. , ++ , .
L "/f-+ AO
L. ,..-+ p+
(9.7)
continuC!l until the energy is no longer great enough to producc nell' particles, and
only sLnble particles remain.

EXAMI'U; 9.3. Calculation of the thfl'Shold energy for 9. prOC\'Sl! in which a projectile
Thus n~ high energy the collisions between particles are not elastic. The particles colJid..'!! with a target at rest in the laboratory, re~lIlting in ~c\leral new particles.
 -
Fundllmmlal parlicltl (9.4 9.5} The conurroliOIl law, 397

According to Eq. (i.5), the magnetic momcnt of the AO ~hould be written as
M ,. - 9~ (~/2I11 N S,
where g.\ 15 tile gyrornagnHic ratio of the ,,0. I t is customary, however, to write the mag
nctic moment in the form
M A - g.l.(lI1p/II1A)(~/2111J1)5 - jJ.A(e/ mp) S,
and the quantity sought e~perimentally is "..\ - igA(m p/ mN, whie~ gives the ,,0 ,~g.
netic moment in nuclear magnetons. I II the presence of a ~ag!,e lle field 03 there IS a
torque T _ M AX cR, so that the equation of motion of the spm IS d5/ dt - T or
on the basis of the GeJl-!\[al\n "eightfold\\"II.Y~ theory (Section 9.8) is - 0.95 nudesr
magnetons. The magnetic moment of lhe A0 had been previously measured a t Brook-
ha\'en, Argonne, and the Uni"ersity of California, using somcwhat similar methods. The
resull.$ wcrc, respectively, - 1.5O.5nm, OO.6nm, and - 1.39O.7nm. The
most rccent me!L'lurement ( I (06) by Hill and his eollaborators at the Brookhaven "ational
Laboratory is - 0.73 0.16 nm.
9 .5 T h e Co nllf!r r:-ut;o n '~ U 'f"II
I n all the processes illustrated in the previous section, it. hl\8 been found that the
following oonservation Jaws hold without. exception:

(1) Conserv:ltioll of mom(!ntulll

(2) Conservation of :mgulnr momentum
(3) Conser vation of energy
and 5 precesses around 03 with an angulnr velocity (4) ConservaLion of chnrge
0. _ - "'A(e/ III D)cR.
Within the limitations imposed by these four conservation laws, :It fil's~ sight
If "'A is negative,Swill prete8l! around 03 in the sense shown.by the arr~ w marked A in the fundamental particles apl>ca r M a wild group of physical entities tending to
Fig. 9-13 and in tilc opposite sense if "'A is positive. After a t~me t the Spill 5 ilas rotated tT:l.nsform into one anothe r without any apparent order in these processes. We
I!.II angle II _ nt. If u is the velocity of the ,,0 and I tile distance moved through the may undcrstand, for example, that the electron and the positron nrc stable because
magnetic field, we have I - 1/11, and thus t here are no other lighter charged particles into which they might. decay without.
violaiing charge conservation. But why is the proton stable find why docs it not
8 - "'... (~) "" .
m, '
(1).9) decay, for example, according to the seheme p+ __ 11' +
tain processes-,:>uch as "")' -.. e- +p+, A __ +
+v? Why is it that cer
+
p- 11'+, or 11'+ p+ __ E+ 71"+, +
Thus if one can obscr\'e 8, one can dctermine".r. in terms of kn?wn q~antities. which comply with the abovc conservation laws-do not occur in nature? Why
Actually the mOlit interesting (and difficult) part of the experiment I$lhe measu~ment d o the particles have such an al>I)."lTCntiy random mass s l>cctrum?
of 8, which requires determi,.illg the direetion of 5 after t~e .1.0 tr~verses the magnetic field. The situation is similar to that of an alchemist in the :\ Iiddle Ages Irying to
One can measure the angle 8 by observing the angular d~trlbutlO.n of .the produc~ of the understand ehemical reactions without. knowing atomic or molecular structure.
A0-dccay. A et&ek of photogral)hie emulsions are placed I~ the dlreetl~n of the A beam, Physicists today are activciy struggling to find some order in lhis apparent chaos.
!L'I ~hown in the figure. :\Iany AD's dccay in the emulslolls, accordlll~ to the pr~eS8 Fortunately, a. ecrtain degree of o rder hM been brought about by the disoo,'cry
A0 r- + p+. Iloth dccay 1)I"o<lucI.$, since they are charged, I.cave tr.ack~ III the emuli!l()n!.
-0
of lIew eonsen'alion laws which resemble lhe \nil' of cOllservatioll of charge rathcr
+
In the decay .10 _.,,- p+, the pions aTe distributed amsotToplcall y (bu~ symmetri- than the first three conservation !:III's. These laws are:
cally) relative to the dircction of 5 in the (,'_frsme of reference Of. ~h~ Ao: Given th~t.ofI
is the angle betweell the momentum of the.,,- and 5, the allgulaT distributIOn of the ~ III (5) Consen'ation of leptons
+
the A C-frame is found e~]lerimelltally to be. proportional to I k cos ofI, corr.e~P:Ond~lIg to (6) Conservation of baryons
a strollg maximum in the din'ction of 5. li enee, by analyzing the a~gular dlstrl.but~on of (7) Conservation of isot.opie spin
decay pions in a beam of p.olarilCd AO's, Olle can ddermill~ the direction of, ~lar"Ulol.'. of
(8) Conservation of strangeness
the AO, which is the direction of S, and ill thill way obts.lII the s.ngle II: I he.n, appl) mg
Eq (9 I) one can find jJ~. The actual cs.lculuions require a careful COIISlderatlon of quan
We shnllnow briefly discuss each of these laws in tUI"II.
t.iti~e ;cr:rred to the laboratory and to the A-centcr--ofmass frames. ]:he value obt~incd
at CERN was ,.. ... _ - 0.5 0.28 nuclear magllctons. The value predicted theoretically EXI>cril11ental data lead to the conclusion tlmt I1lCflO ns and photolls Cnnd in gen
end all p[lrticlcs of spin 0 or I) can be produecd or lumihilated in nny number (this
Bccause of the eliergiC8 involved, we must perform the ca\Cul~t~o~ by mcan.s of .re.la. is one of the reasons for culling them bosons). On the other hand, leptons und
tivistic mechllllics. For simplificfltion, however, IIe. use n nonrelatJ;'ISUCcalc\~I!Luon II hlc~ baryons are restricted with rcgard to the number which may be produced or
givCil the correct rCilult (insofnr u the value of fJ IS concerned) II hen the A moves ller annihil[lted in a single procCS!!. For example, the proccs..~ of electron pair production
pendiculsr to 03. +
"")' -.. e- e+, in which two leptons-an electron and its :Ultiparticle,!l. positron-
 -
398 Pundam fn/o l particlel (9.5
nrc created out. of a photon is possible. But the l>r0ce5S of c!cdron-prCllon produc-
+
tion 'l' ---+ e- p+, which could comply with the first four conservation laws, docs
1101. occur. I n t his process (which is lIo t observed) only one lepton and one baryon
arc I>roducc<i. It is c:q>crimcntal facts of this kind which form the basis for the
fifth find sixth conservation luws.
w u sermliOlI of lop,01ls. Let. us introduce a leptQ!! quantuin numbtr .c de-
fined such that , = + 1 fo r lepton ImrliclC!S and.c = -I for ICI)toll nntipn rticlcs.
Non-lepton pttrticlcs havc zero lepton !lumber. T heil
+
Considering some examples, we have thtH, in the process 'Y - 0 c- c+, t he lcp-
tOil n\lmber 011 the left is.c = 0 and on the right.c = + 1 - 1 = 0. However, ill
the nonobscrved process" -> c- + p+, we have.c = 0 on the left and J.! = + 1 011
the z'ight, so that thc conscrvation of lcptons is violated. The law of conservation
of ICI)tons requi res that Eq. (8. 14) be written in the fo rm
n-op+ + e- + i
J:, = 0 0 +1 - 1 (9.10)
to fISSure n to tal lepton number of zcro on both sides. Thus eonservntion of lep-
tons f"(!(luircs that, in ,6--decay, nn antinCUlrino v ana 110t a neutrino be cmitted.
We must also write E{I' (8 .li) in t he form p+ + ii -0 n + c+, with a 10tallc pto n
number I! "'" - I on both sides. This is why, in thc Cowan- Reines cxperimcllt
(Exam pic 8.G), it was an anti neutrino which was detec ted. Note that Eqs. (8.1 5)
and (8. 1(1) for /'i +-dceay and elcctron capture rC{luire a ncutrino to obey lepton
COIl8(;'rvn tion. By cxamining the decay schcmes of 'L';l,ble 9- 2, thc s t.udent should
verify the law of conscrvation of leptons in cach CMC and justi fy the fact that an
anti neutrino is indicated in somc cases.
Lc~ us mcntion in pa.',sing
. the fact that reccnt (1002) cXllCrimental evidence
seems to suggest that the ncut rinos resulting from pion decay are not identical to
those produced in muon decay or in/'i-decay. The cxperimcnt performed by lL groul)
from ColuU1bi:1 Univcrsity wo rk ing with Brookha\'e n Laboratory's Al tcrnati ng
Crlldicnl Aceelcrator is showlI schellllLtically in Fig. 9- J.!. A hcavily shiclded
"l>f1rk chamber was eXI){)SC(1 to thc antineutriuos resulting from I)ion dccllYs accord-
illg to 11"+ -0.'1+ + ii. T he I)ions had been I>roouced by high-energy protons stri king
fI cmwenient target. T he :UI!iucutrinOij colliding with thc nuclci in thc i<1>ark cha m-
ber, if thcy were identie:,l to those produced in /'i-decay, could prod uce either one of
the reactions p+ + ii -> 11 + c+ or p+ + +
v -0 11 .'1 + , 1 [owever, if thcre were t.wo
kind!;! of neutrinos, only the second retICtioll sho\lld be allowcd. Aftcr n. run of
i!Cver:11 days, in which :111 cslimnted 10 14 :lILtineutrinos p:1SSCt1 through the s park
chambcr, about;,o procc:;scs \\crc oh;,crved in which muons were I>roduccd ; but no
I>o~ilrolls were ob;;crved . This suggests t h !l~ the first rellc tioLL is fo rbidden, and that
the neut rinos produced in pion decllY arc not the sume as those produced ill /'i-decay .
9.5) 399
SIC!'I
. bicldinl!:
Fig. 9-11. Schematic diagram of the ...~)(pcrimcnt. St>ark chamber
dCl('('/.Ot
T herefore it is now usual to write
11"- -0.'1- +,,~, 11"+ --+ .'1 + + ii~,
.'1 --0 e-+ v~ + ve, + +
,u+ -0 -e+ ii~ Ve ,
n-o p++e-+ v., p+ -Oil + e+ + v.,
p++ iie--+n + c+, p+ + ii~ -0 n + ,u+,
where v~ designates the IIcutri no associated with the mUOII in I)ioll decay and v.
thc neutrino associated with the electron in muon or nucleon decay.
Conscr l'aLio ll of oo ryOtu. Defining a baryon qualltum lIu~r b such that
b = + 1 for all baryon particles, b = - 1 for all baryon anti l>artiC\es, and zero for
all non-baryon l>art icles, wc may sny that
ill any proce8lS, Ihe lolal baryoll 1lUmber must remailt tH1Chall!1ed.
T he student may verify ~hnt this law is satisfied in all proce!lSCS previously mcn-
tioned involving baryons, such I\S Eqs. (9.2), (9.4), (9.fI), (9.6), and (9.7), II.'l well
as in the decay schemes of 'fable 9-2. Sincc the prot<m is the lightest of all bary-
ons, its decay into lighte r I)llrtieles (which canllot be baryons) would violat.c the
law of conservation of baryons, and this explains why the proton is a stable par-
ticle. Thus the wo rld in which we livc is, to 11 certain extcnt, the result of the
laws of conservalioll of leptons lLnd b.'I.ryons.
Collscn ;fltio/l of iSOIOIJi c ~IJi" . In Fig. 9-2, the plLrticles a nd antiparticles
we re gro upcd according to thcir 1llM8CS or rest energies. Whcn we consider only
those particles affected by st rong intemctions (mesons and baryons), we note that
they occur as /Ilulliplet8; that. is, singlets (!)o, n -, AO), doublets (K + and K O, p+
and nO,;::o and ;::-), llUd triplets (l: +, 2;0, and 2; -, 11"+, 11"0, llnd 11"-) ' . This suggcsts
that wc may qualify caeh multiplet by a new quantity, called isolQl)ie 8pin T, such
that 2 T + I gives the number of p..'1rticles in ench multiplct. T hus T = O,!, I, ...
e The ,.0, being identiesl to itg IIntil)uticle, has been placed in lhe center or the diagram
and the J!('t r +, rO, r - must be considered in II special way.
 -
Fundamtmlaf parliclu (9.5 9.5) Th~ conurrolion /aWl 1.0/

TA UU,: 9-3 lsolo pic S pin ('T, 'T.), S tra nge neu (.;I.), a nd It seems that t he strong or nuclear
lI ypcrehargc (11) or Meson s a nd Baryo ns- interaction is charge independent. For
example, there is ample experimental evi-
Particles T T. Y dence that the nuclear interaction for the
pairs p+ p +{'T. = + 1), n p+('T. = 0), (.)
.IltWII~
and n n(T. = -I) is the same. There-
"'+, ... 0, ... - 1 (1,0, - I) 0 0 (,bC):-~T, - 1
K +, KO

"
Bar/lolU

0
<to - .)
0 ,1 1
0
fore the strong interaction is independent
of the total value of Tz for the interacting
particles. Thus tM strOllg interaction
p+,11
A'
l; +, l;o, 2: -

0
1
(i. - i )
0
(1.0, -I)
0
- I
-I
1
0
0
betuun tlCO parlicle, depelUi, only on their
/oUll Uotopic spin T.
For example, in the .s<:attering process
o 500
....,ne!"KY,
1000
~leV
';00

+
-.-
";"0 ";" -

n-
!
o
(I, - .)
0
- 2
-3
- I
- 2
7f+ + p + -+ '/1'+ + p+,
F ig. 9-1 5. C!'1)IlS section for (.11.)",+
and (b) ... -+ p+ collisions
of energy.
p+
\l8 a function

we have T. = f' necessarily correspond-

The st rallgcnc3lI lind hyperchnrge of IIntiparticles have gign~
Ollpositc to tho~c of the corre~ponding particles. l\Ieoons and
baryons arc frequently designated by the common name of hadrOl18.
for singlets, doublets, triplets, find so on. We use the word ~isotopicn because T
refers to l)Urtiell!S which have prllCtically the SAme mass and spin and thus occupy
the Same place on a mass scale. - We may note that T bears some rcscmblanee to
an angular mOlllentum J, which may have 2J + I orientations in space, each
characterized by a value of its Z-eomponent J .. and this is why the name ~spi n w
was given to'T. Thus we may consider the isotopic spin as a vector ill a certain
representative space called isotol)ic spin space. The vector has a length VT('T + t)
and it has 2T + I possible orient-ations relative to the Z-axis, corresponding to the
possible values of its Z-component given by T z = T, (T - I), ('T - 2), ....
Each particle in a multil)let corresponds to a value of 'T .. with values assigned
in order of decreasing charge. For eXaml)ie, we have 'T z = +; for )lrotons and
T. = - t for neutrons. Particle Ilnd antiparticle muhi)lets have the same iso-
topic spin 'T, but opposite values of 'T . Thc isotopic spin of mesollS Bnd baryons
is given ill Table 9-3.
The total isotopie spin 'T of a system of particles is obtained by adding, in vec-
tor Conn, the isotopic s)ini:! of each particle, using the SAme addition rules n.s for
angular 1ll01llenLUm (Section 3.8). Consider, for example, the system p+ + p+.
T he two l>ilrticles have 'T = ; each, which may :tdd to give a resultant isotopic
spin 'T = I or O. But 'T. = ; + ! = I. Thus a system of two )fotons necei:l-
sarily corresponds to T = I. But the system p+ + n has 'T. = ; - ; = 0 find
thus the total isotopic spin may be T = 1 or O. Similarly 7f+ + p+ may h!\Ve a
total isotopic spin of t or t. But 'Tz = 1 +; = i, so that 'T = " necessarily.
On the other hand, 7f0 +
p+ lind 7f- +
p+, having 'T. = ; and - t, respe<:tively,
may correspond to either T = to r ;.
The names i,oboric , pin and i,o,pin are also u;;.ed to describe Ihi' property.
ing to T = f on both sides of the equation, and the observed cross section
varies with the energy of the 7f+-projeetilc, as shown in Fig. 9- 15, curve (a),
with a pronounced maximum at an energy close to 300 :\ IeV. However, in the
case of
(scattering) ,
(reaction),
we have 'T. = -;, which may correspond to either T :: i or;. The total ob-
served <:rass section is shown ill curve (b) of Fig. 9- 15. The peak corresponding
to 'T = t falls nt praetically ~he same energy as in the previous <:ase of 'IT+ + p+
for the same total isotopic spin, but at about 1000 :\JeV II. S(X:ond l>eak is observed
whi<:h is attributed to the T = t slate.
As a result of the analysis of processes in which strongly interacting particles
participate, we may state that
The conservatioll of total isotopic spin is a rigorous lnw only for strong intcr+
actions but it cnll be violated in electromagnetic or weak interaction processes.
For example, in the observed process 1\0 _ 7f+ + 7f- , we have T = t on the left
and either T = I or 0 on the right, so that 'T is not conserved.
I n addition to the conservation law of total isotopic spin, wc hnve that
lwlh Ihe s/rony and eieclromaynelic inleractio7ls COIl serve Ihe lolal T ..
component oj Ihe isoiopic spill.
This is n rigorous law, followed in all cases, and is fully equivalent to the law of
conservation of charge.
 - ..,
f'ulldamen/ul parlidts (9.5
402
G m servatioll of s troll gCll ess. Another attribute invented to characterize
pnrticlcs subject to strong interactions is the slrallyelless .4., deli ned so that the
charge of II particle in a multiplet is given by
(!Ul )
q = e(T.+ ~b + ;.4.).
The values of .4. llre given in Table 9-3. Particles and antiparticles h:lVe opposite
stmngenes;,. The law of conservation of strnngencss requires that
Ihe lolal sltallyelless S must remain Ihe same ,i n processes due 10 slrony
0/'eleclrOIll(l(jlulic 'illteractiOIlS .
For example, the process 1'1"- + p+ -Jo nO + AO, which complies with all the ot.her
conscrvation laws, is lIot ob:>ervcd because the total st rangeness on the left is zero,
while on the righ t it is - I. However, processes such as 1'1"+ +
p+ --+ Z+ + ]( + and
1'1"- + 1)+ --+ AO + h: o do occur. I n bolh cases the tOlal stra.ngencss remains equal
to zero_ That is, in a.ll piolHlucleon col1i:,;ions (a system having zero strangeness),
hyperons must be produced in pairs with C{lual but opposite strangencss, a phe-
nomenon called associaled 1lroducliol! . Actually it was the consistent observation
of the associated production of certain hyperons which provided the clue to the
In\\" of conservation of st rangeness.
t'
The conservation of strangcnes;, is not. rigoroUS law; it. can be violated by weak
interactions which allow u. change of strangenes;, of-l. In most bMyon dee:tys
(Table 9-2), the conservation of st rangCllel;s is violated, indicating that the deenys
tfike place by menm; of wcak interactions. For cxample,
:::---+ AO + 1'I"- (ol.,) = + 1),
41'1"- + p+ p.s = - 1).
Hyperons cannot decay into baryons through the strong inter:lction with conser-
vation of strangeness, bceau.;;c the Q of such processes is negative. T his explains
why the hype~ns decay so slowly (about. JO- 10 s) compared with the time in-
volvcd in thei r productioll or annihibtion in collisions by means of st rong inter-
nctions, which is about JO-n s. From thc;;e \,"'0 timcs we lllay conclude thM the
strength of the wcnk intemetion i~ about. 10- 13 of the strength of the strong
interaction.
We might mention at. this poiut. that. another parameter which may be used to
classi fy pnrticles instead of strangeness is thc hypefcharye, defined as y = b + .4..
Values of the hyperchllrgc arc given in T able 9-3. The law of conservation of
strangeness can be relllaeed by a law of cOll serv~ltion of hypercharge, due to the
11\w of conservation of baryons and the definition of y.
The new eonsen'ation laws whil:h we have illt roduced in this section may seem
1Ll0re or les;, ad hoc convelLtions to explain the expcrimenta.l facts. However, the
fact that they arc consistently llpplieflble to a brge numbcr of situations suggests
that they have fI deepcr physienl meaning. At. present their connection wilh the
physical properties of particlcs is not well known in all cases, and is fl subject still
open to fu rther research,
9.6) /nrorianct:, symmelry, and coll$errolioll laws 403
fl.6 'nr; .. ritlnCf!~ Sy"u"f!/ry~ and (."onlu!r')tllioR La'''8
Some of the conservation laws we have just disc ussed Clln be traced buck to certain
invarifillee and symmctry properties of physical systems which we shall now
brieRy consider.
Sp (l ce I r(Ul sia tiOIi . Let us l\SSume that space is homogeneous and uniform;
i.e., it has tra nslational symmetry IlL all points. We must conclude then that a.
physic.11 system will behnve the same no matter where it is located in an other-
wise empty space. Using a mo re mathematica.l terminology, the desc ription of
the properties of an isolated physical system is invari:Hlt with res pect to a. trans-
lation of the system relative to a frame of reference. For example, an isolated
moleculc, COIll I}()scd of severul electrons and nuclei, mUf:;t be described in exa.ctfy
identical terms no mattcr where it is located relative to an obscrver. On the other
hand, we knOll" that the totfil momentum of an if:;olated system is constant. Thus
it can be shown that
Ihe cOllservation of momelltum of an isola/eel system is a result of /I'a/M-
Ia/ional i7wariallce of the law8 describing Ihe system.
In sOlne cases the system may not be isolated, but the physical environment
may exhibit certain translational symmetry. Consider an electron placed betwccn
two infinite parallel planes carrying equal OPI}()site charges. Obviously the physical
conditions do not change if the cleetron is displaced parallcl to the planes. We
know then that whe n the electron is set in motion, its momentUlll parallcl to the
planes is constant. (Th is is usull11y stated by saying that the electric field pro-
duced by the charged planes is perpendicular to the planes.) T hus we again filld
that fil e conservation of mome111um in a git'Cn direction is a consequence of transla-
tional ilwal"ia11Ce of the physical conditions in that direction.
Spa ce rol.Olioll . If we assullle that space is isotropic (i.e., that it has rota-
tional symmetry at any I}()int), then the description of the properties of an iso-
lated system must be independent of its orientation in space relative to a given
frallle of reference. .Let us again consider fin isolatcd molecule: the description of
its properties is independent of the orientation of the molecule relative to the ob-
server. On the other ha nd, we know that the total angular momentum of an iso-
lated system is constant. It. can thus be shown that
Ihe C01u;erootiol! of al/(julo r momellium of all isolated syslcm is a result
of !'ola/jo/W[ il!OO!'IOI!(:e of the laws describillg Ih e system.
In some cases, even though (\ systelll may Hot be isolated, the physical system
may cxhibit a certain rotational symmetry. For cxample, a central field of force
has sphcrical symmetry . We then know that, as a resun of the symmetry, the
angular momentum (relati ve to the center of force) of a particle moving untler
centra! forces is constant. If the field has cylindrical symmetry, as in the case of
the force on an electron ill a diatomic Illoleeule or a charged particle in !I uniform
magnetic ficld , thcn the component of the angular momentum relative to the sym-

'114 Fund!Jnunta/ part ide,
metry a.:<is remains constant. Thus we again find that the roluervaiion 0/ angular
monumLum about a givell direction i, a ron3eqtumu of rotational ,ymmetry 0/ 1M
phy,ical conditi(l/I, rtialit-e u, that directioll.
Both t ranslational and rotational symmetry impose certain limitations on the
mathematical form of physical laws; however, this is a subject that we cannot
explore any further here.
Time tran sla tion . Invarisllce with respect to time translation meal1ll that.
if we prepare a physical system and leave it to evolve without external interfer-
ence, the evolution of the system will be the same irrespective of the time at which
it was prepared, or in other words, of the chosen origin of time. Using a somewhat
more elaborate logic, we can sholl' that
the consen!alion of elleryy of an ilmated IYllem il a colZuquellce of the
im'(lriallu 0/ llie lau:, detlcribinglhe tlyslem relalit-e 10 the chosen oriyill
of time;
..
(9.6 9.6) In ll(ll"u:lIlU, .ymme/ry. and conIum/ion /aWl 40'
This invariance means that the interaction must contain the isotopic spins T l and
T 2 of the interacting particles only in forms such as Tl T2 , which is rotationally
invariant, but not as 1",11"12, which is not. Unfortunately, we cannot elaborate
more on the mathematical meaning of the above statement, but ita similarity to
the conservation of angular momentum under central forces is obvious.
010r8 e reflection. Elutramag/letic GIld IirQ/ly ililera.ctiolll remaill invariant
i/ all chargetl are rep/aced by thOle tJ.ith op/mite tligll (that is, q ..... - q), an operation
whieh is called charge reflection. One ean sho\\' that this leads to the conservation
of the Z-component 'f. or the total isotopic spin in those interactions.
No simple symmetry property or invariant behavior has yet been associated
with the conservation of leptons and baryons. T here nre, however, three more
symmetry operations of great importance in the fundamental behavior or matter.
They are: parity P , charge conjugation C, and time revenlal T.
~lirror
;\!irror

that is, relative to a translation of time. The laws of both classical and quantum
mechanies are invariant relative to time translation.
Couge tranll/orlllfl l.ioll. Our fourth (;onscrvation law, that of charge, is a
little more difficult to associate, in an elementary way, with a symmetry trans-
formation and an invariant property. We can show that
charoe conunoaJiOI! i, a resull o/Ihe invarianu of tile lau:, of the elec-
tromagnetic field (i.e., Ma.tU'eli'1 equaliol!tl) with relped. to a "gauge"
tralil/onnation.
We cannot fully explain in this text what is meant by a gauge transformation;
a simple case of a gauge trnnsfonnation is a change in the zcro of the electric (or
scalnr) potential, a change which docs not aflect the c l~ tric fie ld or the form of
~Iaxwell'8 equations. Another type of gauge transformation is a change of phase
of the wave function; i.e. , the replacement of of by eiiljl. This obviously leaves the
probabilit.y density 1",,1', which is the observable quantit.y, unchanged.
Isotopic spin ro lilti o /! . Are there other symmetry opemtions that can be
related to conservation laws? We have indicated that the isotopic spin is conserved
beca\lse of the charge independence of t.he strong intcraction. We can Imt. this
in the same form as the four preceding conservation laws by saying that
the ts%pic Ipill is (ollsert'ed because strOllg illteractiQIIS are ill1Jariant
with re81Met 10 rolaljolls in i80/0pic spin space.
See, for example, J>anofsky and Phillip~. Clauical Electricity and Magnernm, second
edition, Rending, M~.: Addison-WClIlcy, 1962, Section 14-1.
,
,,' p'
, /2L
cR~:
\L'!
Origin.a,J 'Yiltern
L;
Mirror
l __
ima~
.\J
,.) '")
Fig. 9-16. Reflection in a plane of (a) momenlum, (b) angular momentum.
Po ri ty. This concept, which we considered before in Section 2.9, refers to
the operation or space reflection, either in a plane or through a point, such as the
origin of coordinates. Let us first see the behavior of some dynamical quantities
regarding reflectiOIl in a plane. Consider a particle A ( Fig. 9- 16(.11.) moving with
momentum p. The mirror image or A is another particle A' moving with mo-
mentum I"such that P I = pi, 1'1. = -p~, where II and .1. refer to directions
parallel and perpendicular to the 1)lane, respectively. Next consider a particle
moving as shown in :Fig. 9-lO(b), with angular momentum L. The mi rror image
of A is another particle A', revolving as shown in the figure and thus having an
angular momentum L' such that LI = - LI ' LJ.. = L';.. We sec thell that in
reflection in a plane, p and L behave in different wllyS. For that. reMon p is called
a polar vector and L an axial vector. All vectors that playa part in physical laws
are either polar or axial. The studcnt may verify, by examining Fig. 9-17, that
the electric field is polar and that the magnetic field is axial. FOree is also a polar
vector.
 .. .
'06 Funda~T1I(l1 parlidu (9.6 9.6) lrll'ariarlce, symfMlry, and ronsuwliOri law! 407

~[irror ;\!;rror .\Iirrur

Applied \ ppli<X!
magnetic m""ne!lc
field Held

Original sys~m

(.,
.\Iirror image
Original syg~m .\Error image t I
(h)

Fig. 9-11. HeHection in a plane of (a) electric field, (b) magnetic field.

The laws of classical mechanics are invariant relative to reflection; that is, to (;0) Original 4vstem (IJ) '\lirror im~ge of (al
the parity operation P. In other words, if a given physical system satisfies the
--~---,-')j----- "
classical laws of motion, its mirror image also s:,tisfic8 the \n.ws of motion, and may V180" rotation
occur in nature. This means that in t he mathematical statements of classical
physical laws, polar and a xial quantities must appear ill s uch a way that the rela-
tion among them is not changed by SI):tce reflection. We may thell say that classi-
cal mechanics is invariant to space reflection .
The la w oj conservation of parity states that
Applied
magnetic
parity 18 cOllserved i,l a process if the mirror image of Ihe process i8 field
al80 a proceS8 which can occur in nature.
I
It can be shown that, the j\'[axwell equations for thc electromagnctic field are
invariant to space refl ection, and tha t therefore parity is conserved in electromag-
netic interactions. Physicists used to accept without. reservation the idea that. ail
interactions should conserve parity, even in eases in which there Iras 110 direct
experimental evidence to support the assumptions. So convinced were physicists Fig. 9- 18. The 60Co experiment for
about this property of nature Lhat they were shocked when, in 1956, T . O. Lee (e) ISO" rotation of ~y"!.Cm testing parity conservation in .B-decay.
Ilnd C. N. Yang questioned the validity of invariance under space reflection for
processes due to the weak interaction. T he Lee and Yang propos.1l was motivated fact tha.t they were identical in all respects except the decay mode. Yang and
by what at that time was called the T-O puzzle: Each p:lrtide, described by its cor- Lee proposed that one should accept t.he idea that. the two mesons were identical,
responding field or wave function, is supposed to have a certain intrinsic parity. with well-defined parity, at the expense of overthrowing parity conservation in
T here are good reasons to :I.8sume that. mesons have negative parity (sec Example weak interaction decay. To test the conservation of parit.y ill processes due to
9.5). Looking at Table 9-2, we see that the (posi tive or negative) bon has, among weak interactions, lhey also proposed seveml cxpcrimcnlll.
+
other possibi lities, the decay modes }\ :I:: ---+ 211":1:: +
11"'1' and J( __ 7I" 71"0. We One of the most famous experiments was performed by C. S. WU and her col-
can sholl' (sec Example 9.6) that, if we assume that each particle has a well-defined laborators in 1057 at the National Bureau of Standards. A sam ple of GOCo was
parity, then if parit.y is conserved in the first ka.on decay mode, it is lIot conserved polarized so th,\t the nuclei had their spins aligned (for which it was necessary to
in the second, and conversely. The first decay mode is cullcd the T-mode of decay place the sal1lple in a strong magnetic field and keep it at a temperature close to
and t he second the O-mode (recall Figs. 9-8 and 9- 9). At the first appearance of absolute zero). Then they found (as shown in Fig. 9-18a) that the electrons result-
this dilemma., physicists (to save lhe law of conservation of parity) considered iug frolll the f:I--decay of the /;Co nuclei were emitted in gl'eater qWl1ltities in the
that the two mesons might. be different, each with its own parity, in spite of the direction of the /;OCu SI)ill (or the direction of polarization) than in ihe opposite
 p

Fundammlal parliclts (9.6

' .6) i nrGriana, 'Ymmriry, olld tonltnulian laws 40'
direction. This proved that there is a larger probubilit.y that a lOCo nucleus will
emit a decay electron in the direction of its spin than in the opposite direction.
When they reversed the whole system by- rotating it through 180" nround the
line L, the polarizntion, the spins, and the magnetic field were reversed; the new
experimeHtal situation WIUI u.s shown in Fig. 9- 18(c), with the direction of maxi-
mum intensity of electron emission nl.<;o rotated 180~. On the other ho.nd, the
mirror image of (0.) is showli in (b), where the spins and the magnetic field have
been fCversed, because they are axial vectors, but the direction of maximum in-
tensity of electron emission remai ns the same. Comparison of (b) and (c) clearly
indicates that (b) does not. correspond to a situation found in nature, thus pr(}-
viding di rect e:.. perimental evidence that I)arity is Ilot conserved in weak inter-
actions, which are responsible for .8-decay. After the 6Go experiment, many other Fig. 9-20. DeterminAlion of the helicity of the ,.+.
cxperimcmtal proofs were obtained fo r the noneonscrvation of parity in weak inter-
n.ctiolls. I(owever, it seems that in I)roccsses due to strong (as well as to electro- Cllflrge cQnju g atiQn . This operation consists in replacing nil particles by
Illnglletic) interactions, parity is conserved. their antiparticles without changing any other physical property, such lIS momen-
~tirror
tum or spin.

,J:u ,, S,
lIchclty
+1
A system is ilwariallt wilh regard /0 charge conjugation WJ!CII, If a process
is possible in th e origi'lalsystcm, the correspOlu/illg proc~u is also possi-
ble in Ihe charge conjU!Jat~ 8yslem.

"0 It sccms\hat processes due to strong and electromagnetic inte.ractions are invariant
relative to charge conjugation, and this lends to the conservation of 'T. and thus

Fig. 9- 19. The nonconscntltion of

~lJs. +1
also of S. However, processes involving weak interactions arc not invariant rela-
tive to charge conjugation. T o u,;c pion decay lIS nn example ( Fig. 9-21(a, the
parity in ...-dccay. 1,. chnrge eonjllgate system (Fig. 9- ZI (b) canllot occur because the llntineutrino
would have the wrong he.licit.y.

As a second c."\:dmple of the rlonconservtltion of parity, consider the pion decay lIelicity f PI'
11"+ -- ,1.1 + +~, shown in Fig. 9- 10 (11). The pion has zero spin and, in order to
conserve angular momentum, thc Sl)ins of the muon and the neutrino mlL~~ be in
- 1 lJ<P"
S, ,

opposite directions. Also, to conform with the hclicity of the neutrino, their spins
must be as indicated in the figure (also recall Fig. 9--3). However, the mirror sys-
tem, shOll"n in Fig. 9-19(b), docs not occur in nature becanse the neutrino would
6
,,
have the wrong hclicity. Actually, physicists concluded thnt the neutrino hIlS
negative helicity because of the fact that in 1I"+-dccay the ,1.1 +'8 consistently have n
Fig. 9-21. Application of charge
conjugtllion to lhe ...-d~ay. - 1 s~~ .
negative helicity. If the neutri no could have either positive or negative heJicity,
the,u+ would also have positive or neg:ltive heiicity, in about the same proportion.
L.
In such a ease the mirror imuge in Fig. 9- 19 would corresr~ond to an observed (a) Originat deftlY (b) Chnrltl! oonillltllW decay
process, and pari ty would be COnserved in pion dccay. A typical c)(periment by
which the helieity of the,u+ is determined is shown in Fig. 9-20. The positrons
Rcccnt eXI~rimellts, p-erformed at Brookhayen and CER::'\' on the rlceay of .,0 into ...0,
emitted in the,u+ decay arc always moving at almost 1800 with respect to the origi- ... +, and ... - , have been analyzed for l)()SSible asymmctry in the behavior of the ... + tlnd
nal 1II0tion of the ,1.1+, and have positive helicity (Ii. = + 1). Thus, to conserve ... - The eX]lerimental resulls have proVOked discussions about the noninvariance of
angular lllomentUlIl, the helicity of the other partieies should be as shown. elect romagnetic interactions with resp'ect to charge conjugation. The mlHler, however,
has not been .sell led at the time of Ihis writing.


9.0) IIIM,.iaIlU. ,ymmtlry. and collurm /iQII /aWl 411

41O f'undamtllial parlic/u (9.6
\>"illlli ~lI.IC [lIiO/l1 SI~IC
\[irmr
.,

,luS
.,
II~:'I:

.aJ: ~ 0
0

c).
' 0
0

c)
S~LJ
l 0
0

c) ..
1'.
lIe1irily
+1
[niliAI .!:tw.

CQUi,OOlI
tell ion
"
Filial Slaw.
.,

Sut
, 0 , .,
-,
0 0
"
t.~S' S.~t..
+,
.,
,. ,. ,. "
(b) Timereversed ~y~t.cm
\~) Orij\;nnJ ,[em), (Il) ';IJaN'-~nCNeo.l .tern)' (~) ChalW' !'Qllj"JIi'J!~ of III)
Fig. 9-23. The T operation.
Fig. 9-22. The CP opemtion applied to T-<ie.:ay.

We sh:lll conclude this section by stali Ilg another importa nt theorem:

Nevertheless, n compnrison of Figs. 9-19 and 9-21 suggests u. new po<'!Sibiiity.
SUPl>Osc that we firs~ perform 1\ space reflection or parit.y operation P on the sys-
tem shown in Fig. 9-21(3) and then perform ft. subsequent charge conjugation C,
as shown ill Fig. 9-22; the systelll l'CSulting from the combined opcr:ltion (e p)
also occurs in nature; that is, 'If- __ ~- Ii. Thus: + conjugation C. This thcorem i::l tnle even in e!lSCS in which lhe laws may not be
Weak lultractiol!~ (Ire illt'arialll under the combilit<t ep ol>erotioll.
Time r e !;er.'l(lf. What would happen if the direction of flow of time were
re"ersed? Thnt is, if I were changed into -I, would the resulting equations s lill
describe l)(Issible pMCe>SCS? Under time reversal the (IUnntilies velocity, mo-
mentum, and nugutnr momentum are reversed and in a collision the initinl and final
states are exchanged (Fig. !)-23). Our intuition, supported by strong experimentnl
evidcncc both at the macroscopic and at the atomic levels, points toward invariance
of physical laws relative to lime reven>:11. It is easily shown that lhe laws of classi-
cal mechanics and of electromagnetism are invariant under time reversal. For
cxample, dp l dt is inv:lri:lnt under lime reversal, since it implies the replacements
I' ....... - I' and t ....... - t. Also the electric field t is invariant under time rcycrs..'\lj
however, the magnetic field suffers the lJ":msformation (8 _ - (8 because time re-
versal implies reversing the velocities :lnd therefore also the currents. T hen v x (8
is invariant unde r time rC\'er:lII!, becau.;;e both (actors havc changed sign, and tile
equation of motion of a charged particle, lIp ldt = q( t +
v X (8) , is invariant wi th
re.'il>cd to time roversn!.
SU'ong nnd lI"enk interactiolls lIl"e also considered invariant under time revcrsal,
nlthough lately the problem has been OI>C1l to discussion. Hecent (l90G) experi-
ments regarding a special f0l"l11 of decay of the neutrnl kaoll, which Occur.! in only
0.3% of the cases, secm to indicate that weak interactions may violate the prin-
ciple of invariance under time reversal.
all physicaliau:s m'e cOllsi(iered /0 be invariant ttllder t/ie C PT opera/io/!;
that is, under the combined opcmtions of time reversal T , parity P, and charge
invariant under the individual o l>Cr:ltions.
EXA.\ I1' Lf.' 9.5. The parity of the pion.
&11/1;011: Since the subject is interesting in relation 10 olher calculations, we shall
illustrate how the parity of the pion is det.crmined. Suppo.;e that a beam of r--mcsons
movcs through liquid deuterium. Many pions, afu.. r thcy slow /lo"'n, are Cal)tured by
deuterons and move in staLionary .~tatCS similar to electrouie ~ta1.C8. The syStcl1l$ thll$
formed are called muic a/om,. If the mesic state is excitcd, thc Ilions rapidly fall into the
Is ground state with radiation of energy. In the ground statC the orbital angular mo-
mentum of thc".- is zero. Since the spin of the pion ill ICro, the totsl allgular momentum
of the mesic atom is tha t of the deuteronj that i ~, J _ I. The dimension of thl' Is orbit
of the 11"- is 1/280th that of an electron Is orbit; there ill thus a n~r)' large prob:t.bility
thal the pioll will collide with the deutl'ron. The most prob:t.ble reaction to occur is
(J - I).
111 this process Ilngular momentum is conserved . Therdore the two resultillg neu trons
must also have a total angubr momentum of t. But the neutron~ obey the exclusion
principle, and the complete wave function (orbital X ~pin) of the two neutrons must be
antisymmetrie. The pllrity of the orbitlll wl\ve fUl\etion~ is (-I )1. The tll"O neutrons may
have their spins parallel (S - 1) or antipamlld (8 _ 0). Spin function~ for S _ I are
symmetric and those for S _ 0 are anti..ymmdric (r{'nl('nlbcr 1;,ction 4.2). Then S _ \
must be combined with an orbitlll angular mOmentum I - 1,3,5, ... odd and S ". 0
 p

Fundamtn/oi porlidu (9.6

412 9.6) Inrarianu, sy~lry, and co'lUf'f(l/ion laws 413

with I _ 0,2,4, ... e\"en. The possible states of the two neutron! arc then Let u:no\l; consider t.he decay of the .. +.parti~le, using a frame of reference attached
S _ I: 31'0, 3P L, 31'2, 3Fa, 3F3, 3F~, .. . to tho ... \\ e shall desLgnate the va lue of thc Sp11l of .. + a~ 8,. Using the deeny scheme
S _ 0: LS O, ID2, 104, ... ' + ...
T.+ ........ + + + .".- (t he same result can be obtained using the other decay scheme
gLve n above), we label the angular momentum of the ... + + ...
+ system relntive to their
where, ag usual, the total angular momentum is indicated ft.:'l a subscript T he only slate center of m&.Sil by 1 and use I. to designate the angular momentum r{']ative to the cellt.er
with J _ 1 is 3pL, whieh must then be the state of the two neutron!, corresponding to +
of m8SJI of the whole ~y~tem composed of the C... + .,..+) center of mllSll and the .,; - .
an orbital angular momentum of la - 1. part icle_ The center of mass of the II'hole system coincides ""ith the point at which the
Let ue dCliignalC the paritiCII of the three J}!ortieles involved by P~, P p, and 1'." the orbital deeay of the .. + takcs place. Then t.he conscn-ation of angular momcnLUIIl requircs that
angular momentum of the deuteron by Id, and the orbital angular momcntum of the two I + I. - $., and the quantum rule for addition of angular momenta requires thnt
ne\ltron~ by In. The parity of the left-hand side of the equation is P. P p P n(-l)ld and of
the right-hand $ide p !(_ I )lo. T he conscrvation of parity in strong interactions requirC8
that On th~ oth~r haL~d, t.he yariL?' of the decay products is (_ 1) 3( _ t)L( _ I ) L __ ( _ 1)l +L.
P.p.l'n(- l )Ld _ P~ (_ I)l .
Thus Lf P, IS the mtnnslc panty of the Tmeson and if parity is conserved in the .. +..decay,
But the ground slate of the deuteron hIlS Id _ 0 (with II. ~mall admixture of L:. - 2; see we must hl\\e
Section i .i) , and wc hll\c shown that In _ 1. Then P~P. - - Pa If we assume that P, _ -C- I )I+L _
the proton and the neutron have the !Bme parity (which is plausible, since thcy are dif
ferent charge states of tilt nucleon), \I-e conclude that 1'. - - 1 and the.,..- hag odd Since it appears that the spin of the ..-meson is Jero (" - 0), ""e should have 1 - I. and
parity_ thus 1+ /.. _ even integer, nud therefore P, _ - I. T hUll if Sf _" _ 0 we have
When we talk about the parity of the .,..O.nlcson, we necd a slightly mo re complex t hat P, - - 1', and th? two particles do not have the sallie parity. (If Sf - ;, - I, we
analy~is, based 0 1\ the fact that the .,..- + d+ _ ... 0 + 2no process docs not occur. The r~aeh the same conclu~lOn after a more elaborate consideration.) Therefore the assump-
result is consistent with an odd parity of the.,..o particle. We therefore conclude that all tIOn th.at e an~1 .. part1cles are the same implies that the law of parity conservation hlL!!
pions have odd J}!ority. been "LOlated m one of the two decays.
f;X AMPl. 9.6. Lack of conser\"&tion of parit), ill the decay of the K.~cson.
1600 (2 +)
$o lllt;Oll' Table 9-2 indicates that a Kmcsan can decay ink! either twO or three pions. 1500
].]2U 12 .) 142U(O -)
A s we mentioned previously, when thcse types of decay were observed for the first time,
1310 (2 ,)
physicists assumcd that these decays were due to two different meson~, caUed fl and ..- 13IU (I')
12N ( 1 +)
mesons, respectively. T he decays wcre written as fol1ows : 12\0(1 +)
1250 (2 ')

105O (U)
"100 - 1019(1 -)
S9"l (I -) " 9900 'J
>0 ' IlJS (O-l
700 ( 1 -) 7sall -J
Within experimental accuracy, thc fl and ..-mcsons are identical, at least with respect to
mass, charge, spin, nnd lifctime; therefore the naluralassumptiOIl was to consider them ".1
as the same particle. Thc flaw in that assumption, in 1956, Wall that parity could not be
conserved in one decay if it were conSCfl'c<1 in the other. We shal1 now analyze this_
-.
Working in the frallle of reference of the decaying particle, let WI caU .. the \"Slue of the
spin of the fI+. Conservation of angular rdbmentum requires that the tOlal angular ""
+
momentum I of the ~Y5 t{' m ... + ~ relative 1O the decay point alllo be"i that is, I - ...
On the other hand, the intrinsic parity of Ihe pion is - 1 (see Example 9.5). Thus the Fil!!:. 9-2-1. :\le$011 fCsonnllees. The
parity of the system ... + + .".0 is (_ l )~(_I)L _ (- I)". Given that P, is the intrinsic 137 (0 ") spin and parity of each rC'iOlLnnce i~
llarity of the 8.mcson and that parity is con~erved in the e+ decay, we mnst t hen hal"O gil"en in ]larenthesc.!l._
0
P, _ (- 1)" - +1 if .. - 0,
K ,
1- I if .. - I. ,_ 0 ,_0
Hut there ~ strong e,idellee that III - 0, and thus we should have r. - +1.
,- , .-+ 1
.. I
., __ 1,0
,- 0
9-,tI,O ,- 0
 -
4/4 FUlldam(ll/a/ par/ie/a (9.7 9.7) 415

2190(j-)
3
2I(1C)(!-)

2030 (1') , c
1920 (t-) HllO {i)
CO
B "
1830 lt -) 1815 (t)
181S tP) li67 (j:-)
iti70 (t -) 1674 (t)
1{;60 (;-)

152()(t - ) 1530W)

1405 {t-) 1385 (;+)

1318W)

1231Ht ~)
1193<i') oL---------~----

111[>(!') (.,
"'" 939(t ')

,
, ,
.
800

,-.., ,-. "

.-..
N CO
.
, __ 2
,_+ 1
-1
q _+ l ,O
,-+ 1
- 1
q_+ 2,2o I, ,-
.-. q _ 201,0
,_ - 1
-\
q _ _ I.O
.-
q _ -I

Fig. 9-25. naryon reMnanws.

The spin and parity of each resonance is given in (.,
parentheses.

9.7 R e JlORIIRrC8
T he fund:l.I11ental pnrticles listed in Table 9- 1 cnn all be considered long-lived by
particle standards. In nddilioll to these long-lived particles, in the ItlSt few years
experimental evidence htlS accumulated which points toward the existence of ve ry
short.-livcd particles, called I't80l!allcel. Their lifetimes are so short (of the order of
10- 20 s or less) that they do not leave any recognizable track in bubble or spark
chambers. T hese particles enn be classified according to baryon number, hy per-
charge, nnd isotopic spin, and al'e designated by the same symbols as those baryons
and mesons which have tho same quantum numbers tIS the resonances, but with a
subsCril)t 1, 2,3, ... acco rding to inerensing mass. The number of such resonances
is about 80 if one includes nil charge states and antiparticles; their number is in-
crelLSing eontinunlly. Figure 9-2-1 (set! preceding page) shows some meson re-
sonances and Fig. 9-25 gives some of the known baryon resonances. The ml\SSCs
(ill ;\leV), s pins, and pArities are also shown.
Resonances are identified by a very subtle application of the l>rineiplcs of con-
servation of energy and momentum. Suppose that a partieie A collides with an-
other pnrtieie B at res t in the laboratory, 1'Cilulting in I>artieies I, 2, 3 (Fig. 9-26(a;
thnt. is, A +B -> I + +
2 3. If we observe particle I at 1\ given a.ngle with respect
to the direction of motion of A, we should observe a continuous energy spectrum,
since the conservation of energy and momentum nllow8 different directions of
motion and different. energies of I)artieies 2 nnd 3 for a given direction of motion
of I. Suppose, instead, that the process is in two step.... In the first step, only two
particles are produced; that is, II + +
B -> I C. In the second st.ep, particle C
+
decays into 2 and 3; that is, C -> 2 3 (Fig. 9- 26(b). Since the first process
involves only two partieies, the energy of particle I is fixed for a givel\ direction
of motion and its energy sl>cetrum is as show n ill the figu1'C. I n this case the energy
+
of particles 2 3 is also fixed. Figure 9- 27 showa a more complex situation, in
which five particles arc produced, If 1)''Lrliclcs 3, 4, llnd :; mult from the decay


PWlda~lIl(d
'" porfidtf

We shall now apply these formulas to a particular situation. It i~ ob!!<-n'cd that, in a

(9.7
9.8) JIIhat u a !ullda~nlal parlide? "9
...-.p+ collision, the end products arc oftclI 11 neutron and two photons; therefore we llIay proccSS occurs in two iiWI)8,
wrile the reaction as ,.. + +p+ .... ]J++,..++!)o
"'-+p+-> 11+1'+1'. (9.1S) L.,..+ + ,..- + ,..o

If this reaction occurs in one step (i.I'., if it correwonds to Fig. 9- 2(l(a) ..... ith proper iden- corresponding w Fig.9--Z7(b). III thiii case the energy and momentum of the thrce parti-
tification of the p&rticictl), it is a three-body problem. Assuming that the ... - and the p+ cles result ing from the !)0-d('cay must be consistent wilh those of a l!Articlc of given
a~ both at r(!;lt in the laboratory, the total energy &\'ailablc is mass. Noting that in this CMe we must have

Q - (m.- + /lip - mn)c~ - 139 :-'I('\'. t:.+Bp-E~+f:~+E.,

This energy mllst appear as kinetic cn('rgy of the three resulting pArticles. Since this I'. + J>~ --+ p~ + p~ + I'.,
elll'rgy ciln be diSlribut.cd in a continuous way among the three pllrticl~, the 1)11010113 we mAy experimentally dct('rmine E, and p , by measuring the other quantities, And from
could hM'C any energy Irom zero to almost 139 :\lcV. those values we should be able w obtain the m8$ of the '10. The difficulty is that we ob-
Another alterllatke pr()CeSl< is one whkh oceurs in two stel);!:; that is, serve two..,+ and we cannot tell \\'hich one is the original:l'+ snd which one comes from
t he '10. Therefore, we have 10 make the mass CAlculations for the ,,0 in duplicate, us ing
"-+I)+-U + "O both ,..+'8. The experimental result ~ shown in Fig. 9--30. The pronounced lX'ak around
L,y+y (9.16) a mass cquivalent to 550 "leV, corres!){)nding to the corn'ct "'+, is proof that the process

C01'l'e~r){)nding to Fig. 9- 26(b). In this case the energy released (if the,..- and p+ arc both
has two steps involving fin '10_particle of .~uch a mflS.l!. Thc remainder of tho mass dig..
(ribution i~ due to thc wrong choice of 11 ,..+ in each case. Thus we again see how the con-
at rest in the lrframe) ill servation laws allow us to infer the existence of p&rticle~ whil:h we cannot observe other-
Q - (m.- + mp - m .. - m..,)e l _ " :\Ie\'.
wise.

This energy IIoI)pel!.U 118 kinetic energy of the nand ,..0; ther('(ore, according to the laws of
conservation of ellerg)' and momentum (!lee Appendix II, Eq. A.27), the kinetic energy
of the ,..0 is ,,
E . ,o -
mn
+".m. oQ'" 3.6 ~Ie\'.
We have used a nonrelalivistie formula, since the kinetic energy of the pion is much smaller
Fig . 9-30. Experimental mass of the
than its rest mlloSi!. Therefore thc total energy of the"o is About 138.6 :\ leV, corresponding
intermcdiate '1 0 resonance. If this particle
to cp. __ 31 ~leV, which would be the energy spreAd of the photons resulting from Ihe did not exbt, a mass di~trib\ltion WIthout
pion dceay. The photon energies should then fall in the ronge !(138.6 31) :\leV or peaks would be observed.
from E~2"" 54 "leV to t.:.1 ..... 85 MeV. This is wh:H is observed experimentally, verify-
ing t hat the ,..-.p+ collision i~ a two-step process that takes plal:e according to Eq. (0. 16). )'111M of inu:rmediatf! p,jrtit\c
This example, thcrdore, illustrates what we have said about idcntifying resonances by
meAns of energy-momentum correlations.
!I.II " 'hlll iN " "'"nt/"""-",,,/ 'lIrli,,',P
f;X AMPLE 9.8. Det:lion of the 'la-particle. Now, in light or our prec<xling di;,cu3Sion, are we in a I>osition (0 define Il funda-
ment:l\ particle? We knOI\ th:lt fundamental particles are precise I>hysieal entities
501,,'.ioll' The '1 0-porticle, as we explained in conncction with Fig!. 9--28 and 9-29, hits
chnrnclerized by certain properties such as charge, m:lSS, spin, etc., that t hese
such a short life that it canno~ leave Ineasllrable tracks ill a bubble chnmber. In tha~
respect t he '10-particle behaves like a resonance. Let us consider the reaction pnrlielt!:; interact among themselves neeording to more or less welldefined inter-
nctiuIIH (Htrong, eleetromngnetie, w(',lk, and grnvit:ltion(1), and (hnt (Ill the pro-
ecs;c:; I'hich t:lke plaee llmong these pnrticJc~ follow eertnill eonSCrv[ltion In.ws.
Dutlhere lire ,;t;1I many serious :1Ilt! impo rtnnt que:;tioHs. Why :\T(~ there so many
If all the pions are produced at the time of the collision, the process would correspond to particle:s? What fUlietion in nature docs e:leh of them fulfill? HoII' lire they related
Fig. 9-Z7(a), with no correlation among the energy and momentum of the five I)articles
among thenlsehes? Why do they have certain mflSS and spin \'alues't Why are
ex('('pt that impotled by the overall conservation lawii. Hut the possibility exists that the
they divided into t\\'o \'Cry distinct el:\;;ses, bosons and fermion:>?
 - ...,

What is a JUlldamelllol parli~k?

Fun.damenful particles (9.8
9.8)
'"
, ,
-'' -<" " -,:<"
", >-"-<"""">""> " "">-'--<",
T X 10-1 T X 10-1
(,) 2.0 (,) 2.0
~
.fj 1.5

~ 1.0 Fig. 9- 32. Strong interaction resulting (rom the exchange of pions.

"~
_ 0.5

0.5
+
oh~~:L::::~"'==
1.0 1.5 2.0 2.5 X
,
m 1O-1~
-0.5 -0.5
(a) Proton (b) Neutron
Fig. 9-31. Theoretical radial charge distribution for (11.) protons, (b) neutrons.
In the same way that we look at atoms as being composed of certain basic in-
grcdients (electrons, protons, and neutrons) or of nuclei as being composed of
protons and neut rons, we may assume that all fundamental partieles arc composed
of certain building blocks or superfundamental particles. Gell-i\-fann has proposed
thc nallle quark for these supe rfundamental partieles. Quarks have certain HOVel
prope rties, such as fractional charge (!e or !e). But as yet ",body has observed
quarks, in spite of the intensive hunt that has been going 011. Following another
approach, we could consider, for example, all baryons and their resonances to be
excited states of a basic baryon (we might. use a similar logic for mesons) in the
same way thnt a hydrogen atom mny exist in its groulld stale or in many excited
states, each state having its OWII at.tributes, such as energy, angular momentum ,
and parity. But no satisfactory theory along this line has yet bc<:n formulated.
In any case, what we call fundamental particles do not seem to be by any means
simple entities. For many years physicists have considered a nucleon as being
eomposed of a core-a "bare" nucleon which is unobservable--surrounded by a
cloud of pions, in the same way that an atom is a nucleus surrounded by a cloud
of electrons. T he radial charge distribution of this pion cloud for the proton and
the neutron could be as illustrated in Fig. 9-3 1. For Lhe neutron, the total charge
is zero. (Incidentally, this affo rds a mcans of distinguishing a neutron from all
antineutron, since the antineutron would have the sign of the different layers of
charge reversed.) T hese graphs are similar to t hose of Fig. 3-13 for the radial
The word \\ns taken from:1. rather obscure passage of James Joyce's Finnegan'3 Wake :
ThrCi) quarks for i\luster i\lark!
Sure he hasn't got much of I!. bark
And sure any he has it's all beside the mark.
Webster's New International Dictionary, 1961 , dcfines "quark" ns the harsh cry of the
crow, or any sound imitative of this cry.
charge distribution of an electron in an atom. Ko theory about pion dynamics in
a nucleon has yet been developed, but. apparently the pion cloud may be exeitell
to higher energy levels, giving rise to mlCleon isobars, in thc same way that atoms
may exist in excited electronic states.
Another interesting aspect is the interpretation of interactions as the result of
the exchange of hosons betwccn the interacting particles. An cleetromagnetic
intcraction results from the exchange of photons betwecn two charged particles,
as indicated in Fig. 1- 13. Similarly, it is accept.ed that. the strong interaction is the
result of an exchange of pions betwccn the intcracting particles, as indicated in
F ig. 0-32. The particles exchanged are called virtual becaose they cannot be de-
tecte<! as separate entities. The short range of nuclear forces may be very nicely
explaine<1 with this model for interactions. A proton is not a static system, but is
continuously ejccting and reabsorbing some of its surrounding pions. When a
virtoal pion is emitted, the proton energy changes by an amount
6E ~ m~~2 ~ 140 ~ l eV.
According to Heisenberg's uncertainty principle, Eq. (1.49), this pion can exist,
without any violation of the laws of quantum mechanics, during a t.ime
After this time the virtuall)ion must. be reabsorbed by the nucleon or exchanged
with another nucleon. In this ti1)le, if we assume that the pion travels with n.
vclocit.y elose to that of light, the maximum distance it can go is about lO-H m.
This then gives the nHlximum distance at which a second nucleon must be located
to absorb the virtual pion. T he student shoold be struck by the fact that this is
prccisely the magnitude of the range of the nuelear interaction. When wc think
about the above model of nucleons and their interactions, we sec that it is an over-
simplification to say that a nucleus i~ composed of protons and neutrons. The
best indication that a bound neutron is not. the Sl1me as a free neutron is that
bound neutrons in general are stable and do not. decay.
Tn the case of electromagnetic interactions, we may assume that a charged par
ticle is continuously emitting and absorbing virtual photons. The virtual photons
emitted by charged particles have zero rest mass; therefore thc energy fluctuation
6E of a charge<1 particle may have any arbitrary value, and the lcngth of t.ime that
the virtual photon can cxist before it is l"eabsorbed or exchanged with another
charged particle is also arbitrary. A calculation shows that the force between two
 >

'" ,"'ulldaml'llial parlick$

charged particles resulting from the exchAnge of zero-rust-mass photons must vary
(9.8 9.8) What i.r CI JWldCl~tl/ClI parli&? 423

Solurioll: An imporlAn~ experimen~ ahowing the existence of nucleon excited states

as the inverse square of the distance of the two charges, in agreement with Cou-
lomb's law.
It thus llPI)Cars that pions aTC the cMricrs of the strong interaction. For this
rcn.soll the existence of the gmviton A..'!J the carrier of gravitational interaction has
been postulated. and another particle (a wonk boson, W) has been postulated as
the carrier of the weak interactions. Neither of these particles has yet been
observed.
Although the theo ry of elementary I>urliclcs is still in an imperfect state, phys-
icists have been able (by using some elaborate mathematical concepts) to gain
some understnnding of the relations alllong the particles. Perhaps the most in-
teresting theory is one proposed in 1961 by:\1. Gell-:\lann and Y. Ne'eruan, called
the eightfold way because it. required a set of eight basic operators. This theory
predicts that, among the baryons and mesons, multipiets of eight and ten partieles
should exist with certain relations betwccn their quantum numbers and their masses.
Other groups with a larger number of particles are also supposed to exist. The
theory predicted Lhc existence of the n --particle, which was shorlly afterward
observed (February 1964) at Brookhaven N ntiollal Laboratory (see EXam l)ie 9.10).
T he field of elementary particles is one of the most active and challenging arena
of research in contemporary physics. New and bigger accelerators nrc constantly
being built to cxallline the existing I)roblems, but these accelerators orten create
new problems by uncovering new and unsuspected processes. It is hoped, however,
that in a few years our understanding of elementary particles will reaeh a status
similar to our understanding of nuclei, atoms, and molecules.
( tha~ is, nuclwn isobars in "'hieh the pion cloud has been raised to an exeitA!d energy
statA!) is the analysis of prolan-prolan collisions. The experimental sctU\1 appears
in Fig. 9-33(11.). Proto ns from an accelerator hit a liquid. hydrogen target. Those
protons which are scattered th rou gh a fixed angle (J pass through a magnetic field <8,
whi ch deflec ts some of the protons through an arc of a circle of fixed radills r, determined
by the initial di rection of motion and the position of the detecwrs VI and Vz. This allows
WI to dctermine the momentum of these protons, given by p - e<Br. Ily vsrying the i.n-
tA!nsity of the magnetic field, we ean change the momentum of the protons passing through
the fixed deicctoTl:l and analy;e the momentum distribution of the scattered protons. The
experimental result is shown in Fig. 9-33{b). In addition to a main Il.eak in the momentum
distribution of the protons (corresponding to elastic scattering by the target), there are
severa.l secondary peaks, corresponding to protons of lesser momentum or kineti c energy.
These secondary peaks corresllOnd to inelastic lICatiering, in which the incoming [lrotons
lose some of their kinet ic energy to a target proton, which ;$ raised to an cxcited isobaric
alate of well-defined energy. The student may reeogn;.re the fact tha.t lhi~ experiment is
similar to the Franek and Hertl experiment of inelastic electron-atom collision, which
showed the e:dstellce of excited stationary atomic state~ of well-defined energy.
EXAMPLE: 9.10 . The omega.-minus experiment.
5olu l;(>II: According to the ~eightfold wayN theory of Gell-i\lsnn, Ilarticles should be
grouped in families, with all members of a family having the same Sl)in lind parity. If
we look at the resonllllCCll shown in Fig. 9-25 and plot the fllmily of len lighter particles
having spin j- (and positive pllrity), we obtain the arrangement of Fig. 9-34, which ex
:\1","" :\1eV

Stlllntel\C!lll u-
EXAMPLE 9.9. Inela.stic lICaU~ring of high-energy protons 8!1 a result of proton-proton -3 o , 1676
collisions.
,/
Incident Liquid hydl'Qll:ctl ,/
prown~
b"" 'E. -/
,
I
,, '''''
"
-2
,,
, ,, ,
[:;:rlt1~ ,,
Elastic !lCttU('rinjl: peak
,,
Shiclding
-, .,
~ , ,
,.
,I
<as.;
,,
..aU :\Iagnetic
field
I nelruitic peakll
,, ,
,/
,
, ,/ "
,
,,
,
from proton
exeitntiotl ,, /

Oeflected
i
~L-~ __________~~~_ f.
" L-__
J.i J.G/
I
,

-;"/CL____-1,_--'''~----_!,_--"'~----~----'"'~----~
1238
a ',/
I i

protoll8 i\[ornentul11 Qf M'lOttc~1 prolQl1$ / -t - -i t / f

,., ,b, q/~
I
__ l
J
I
0
/ n
I
+J
/
I
+2
r,

Fig. 9-33. (a) Schemslic disgram of proton-proton inelastic lICaltering e)'IlCriment. Fig. 9-3-1. Arr3llgement of lighter hyperons with spin f lind positive parity, following
(b) Experimental results showi ng incb.slie scattering Jleaks. Cell-Mann's eightfold way.
 p

424 F'undOl7ltflluf porlicftl (9.8

9.8) Whot i# 0 /UlldallKlllaf parlicle? 425
hibits a nice g{'(lmetrical symmetry. At the time of Gell-Mann's propo~al (1961 ), only
the 6-quartet and the 2:-triplet were hown. But shortly afterward (J D62), the :::-doublet
was rel)Ortcd, and it fitted well with the scheme. From the regularity of the pyramidal
structure it wa! easy to predict that lhe rcmaining particle at the tOI) should have T . - 0
and T _ 0, and thus be a single~. Also its strangeness should be ... - -3, giving a charge
-e according to 1-:q. (D. I I). Finally, from the regularity in the mMS differences lJ. - l;
and 2: - :;;:, it could be inferred that the new IlIlrticle (called n- by Gell-:\lann) should
ha" e a me& abo\l~ 1675 :\leV. This therefore fully idcntified the missing particle. (Gcll-
:\Iann's prediction IO' M! ba!!(!d on a more serious theoretical basis than this si mplc
geometrical arrangl'menC) Jo'rom the;:c Ilrop'ertiCII eXllCrimcntcr;! expected, in view of the
,, ,
conservation laws, that the f1 - could decay into :;;:0 + "'--, :; : - +
,,-0, or AO +
R -; this
meant that, by observing the dN:ay prod ucl.s, they had a clue by which they could
identify this particlc,

I'rol()n
bellm T arget
&'
...... '"
/
Shielding

"'-'-----Il5--~
,y DeAecting nnd
focusing mugncts
K-, " -,1' - \ Slit

"-
K- Bubble
chllmber ,. '"
Fig. 9-36. I'hotograph which first showed fI - particle production. ( Photograph eourtes~
Fig, 9-3.), Schematic diagram of the fI - experiment. llefore the !!Cparation there were
Brookhaven National Laboratory)
a[lproximately 800".-- and 10 ii- for e"cry 10 K - particles. After !!CllIlration, there Willi
only one.,,- and no ji - for every 10iZ - -particles.
menter1l had obtained about 50,000 photograllhs, of which one (sho....-n ill Fig. 9-36)
corI"C8I)Onded to a process in which an n- had been produced. The trend of processes in
The lIe.~1 step W/lS to see if the particle could be produced and obscn'ed in the Inooratory. Fig. 9-36 is as follows:
A possible Ilroduclion proceS8, comrl.l!.lib1e with the coMCr"atioll laws, would be
(Vertex 1-")
(Vertex E)
In 1963 an experimental selUrl was prel)arcd at the Brookhaven Xational La boratory. (Vertex D)
A 33-GeV proton beam gellerated by the accelerator hit a tungsten target, ]lToducing (Vertex C)
R - -mC!!on!, together with ]liOIl8, antillroton!, and other particles. To extrad the R - _
(Vertex B)
mesons, the eXllCrimelltcr;! devised all ingeuious arrangemt'llt, ~ho,,"n in simplifit>d form
in Fig. 0- 35. For ('xllCrimental conven ience, they cho~e R-'s with a kin etic energy of (Vertex A)
5,0 GeV (which is well abol'e the thr('~hold energy of 3.2 :\lcV of the procel!o8) and ex-
tracted them from the accelerator tu be by means of a defiecting magl\ct. The extracted Of Course the neutral particles do not leave any track in the chamber. The photograph
beam, in addition to contailling R - -pnrticles, was composed of a large number of "11"- is analyzed at the right in Fig. 9-36(b). From vertices A, B, and C the energies, moments,
and II. few V-, .!IO the next tMk was to separate the 1\--particlc8 from the otlwr Ilarti c l(!~. and directions of motion of the A0 and the two "')" 1\ are found, thus locating vertex D and
This was accompli~hed by mean~ of a s(!cond set of deflecting and separating mllgllet.s, the energy, momentum and direction of motion of thc :::0. Finally, llSillg the previous infor-
together with a slit arran ge ment. Next they allowed the almo.;t pure X - -beam (it COIl- mation, the expcrimelllers could compute the energy an d momentum of the n- from the
tained only abo ut 10 ]l('Tc('tlt .,,- Rnd 110 antiprotons) to enter n shielded 2-m bubble data. at "ertcx E. T he analysis gave a m!l1!8 value between I668McV and 1686 MeV.
chamber containing liquid hydrogen, ill which the reaction producing the f1 - ~ould take A lICCond photograph, obtained a few weeks later, narrowed the mass to the range
place. Tht' tot:ll length of th!' path of the X -'" from the target to the bubble chamber between 1671 and 1677 MeV, in excellent agreement with the theoretical prediction.
W!l1! about 135 m. After a rUIl of several weeks, by the end of January tOu1 the experi- The length of the n--path in the chamber was about 2.5 cm, ~ howing thal the fI- -life-
time is about 2.5 X 10- 2 m/3 X 108 m 81 - .... 10- 10 ,.


427

8tituting a mts1c alom. Al!3u me that \\'e 9.10 Find the magnetic field for lhe chosen
can compute the ener!,)' and the radiu.~ of value of the p--momentum in the anti-
Evolution of the Physicist'll Picturc of Nature," P. Dirac, Sci. Am., May 1963, the mewnie orbit by lhe same formula.s proton elCllCriment (Example 9.2).
used for electronic orbits in the hydrogen 9.! I rn t he 11'0 ...... l' + l' process, eonsidcr
pagc 45
atom (E)(ample 3. 1). (a) Wha t energy i~ the ea.sc in which the two photons are
2. "Early Work on the Positron and Muon," C. Andcrson, Am. J. Phy, . 29, 825 (1961) released when a free pion at rest is cal'"
3. ~Thc Rolc of Elementary Particle Research in the Dcvclopment of ) I odern Phys.ics,
emitted in the C-frame in a direction per-
t urcd into the ground state around a pendicular to P . (in the I.... frame). Show
V. WciSlIko pf, PhI/tic. Today, June 1963, page 26 proton? (b) COffi[)ute the radius of the
4. "Particles and Principles," M. Gell-Mann, Ph ytic. Toda y, Novc mbe r 1964, page 22 groundstate orbit of a pion moving around
that in tho Lframe their energie~ are ;E.
and that they move at an angle with " ,
1\ proton. (c) Estimate the nucleus for
5. "Thirty Ycars of ~le80n Physics," R. Oppenhcimcr, Phyrie. Today, Novcmber 1966, give n by t8n- 1 m,e/ p.
page 5 1 which the radilL'! of the ground-state or-
bit of thc I)ion is equal to the radius of the 9.12 A ... omeson having a kinetic energy
6. "Resource Letter SA P- I on Sub8.lomie Particles," C. Swarh, Am. J . Phy' , 3 1, 1079 nucleus. in t he I,-frame equal to its rest energy dc-
(1 966)
9.4 A neutral kaon with a kinetic energy cayg into two photon~. Suppose that, in
7. "The Conservation Laws of Physics," G. Fcinberg and M. Goldhaber, &i. Am., the C-frnme, the photons are emittcd at
of 100 tl l eV decaYll in flight into two op-
October 1963, page 33 angleg of 30" and 210, respo(!cth'ely, with
positely charged pions. The kinetic energy
8. ~Violalion of Symmetry in Physics.: ~. Wignef, &i. tIm., Deeember 1965, page 28 the direction or motion of the ...0 in the L-
of one of the pions is 200 MeV. Comllute
frame. What are their energies and the
9. " Resonance Particles," P. Hill, &i. tim., January 1963, page 38 the momentum of each pion alld the angles
their paths make in the IArame. angle made by thcir directions of motion
10. uQuarkways to Particle Symmetry," L. Brown, Phytic. Today, Fcbruary 1966, in the I,-frame?
page 44 9.5 A nelltral KO_meson is ob.scrved to
decay into a I)air of oppositely charged 9.1 3 Consider the decay of a 'lr0-meson
II. "L'nified TheOries of Elementary Parliclel, S. l3Iackman, l'hytic. Today, February pion~. Initially the pion tracks are per_ into two photons. Given that the photon
1966, pagc 5.5 pendicular in the L-frame, but are bent by energil'll afe t.l and 11'2, show that they arc
12. Structure of Maliff, W. Finkelnburg. New York: Academic Press, 1964, Chapter 5, u. magnetic field of 8.5 X 10- 1 '1', so that
related by
Seetions 20--26 they have radii of 0.8 m and 1.6 m, rcsllCc-
E'd:2 - ; (m .c2)2/(1 - cos 8),
13. "Symmetry and Conservation U\\s.," E. Wigncr and "Element.ary Particles," G. tively. CaleultLle the relit ms.ss of the KO_
Chell', published in The Scientific Endw,ffw. New York: Rockefeller Institute, 1965 meson and its kinetic energy. where 8 is the angle bt-tll'ccn the I)hoton
14. Tht Fel/nman Lutl.re, on Ph!l~iu, Volumc I, n. Feylunan, R. Leighton, and M. 9.6 Determine the Q.valuc and the pro- directions as measured in the I,-rrame.
Sand~. Reading, Ms.ss.: Addiwn-Wesley, U)63, Chapter 52 jcctile threRhold energy in the IArame for 9.14 A I)('am of negative pions (... -) enter-
15. The Fundammial Parlielu, C. Swart,;. Reading, :\Iass.: ,\ddison-Wesley, 1965
the following react ion.'!: ing a bubble chamber triggers the reaction
16. E/trlltnlar!l Pattie/u, D. Frisch and A. Thorndike. New York: :\ (omentum Books, "'-+I)+-.Ao+Ko. The luccc;Il\ive
"'-+p+-.AO+ Ko, decay processes of AO and KO also take
Van Nostrand, 1964
P+ +P+ ...... II ++ n +.,..+, placc within the chamber. A Olngnetie
17. Partiele, and It cceltrator~, R. Gouiran, World Ullivcrsi~y Library. New Yo rk:
1)++ 1)+ ...... p++AO+ K +. field is apl)lied in the region occupied by
:\IcGraw-HiIl,1967 the chamber. !\lake a diagram showing
I n eleh case the projectile is the firsL the whole process. Neutral 1)lrticles
particle. The second particle is the target, should be rellrcsented by dashed lilles and
EWsumed at rest in t he laboro.tory. ehl!.rged particles by continuous lines with
"roblf'"'''' the proper curvalure.
9.7 Calculate the minimum kinetic energy
of the incoming proton necessary to trigger 9. 15 A 1-~l e V Jlositron collides with an
9.1 Compute the radi lL'!, energy, and 9.2 tlluonium is formed when a charged electron which is at relt in the I....frame
.I'-mC!!on and an electron or I)()l!ilron cir- the process shown in Fig. 1)-12.
angular \'elocity of lhe ground-state orbit and the two annihilate. (a) What is the
of positron ium. Also determine the first culate about each other. Dewrmine (a) 9.8 Determine the energy of the photon
energy, in the C-framc, of t he two photons
excitation energy of positronium. How the energy and radius of muonium in its in lhe process ... -+ +
1)+ ...... n 1', when
emitted? (b) Given that one photon is
many revolutions will positronium make, ground !llale; (b) the dissociation energy both colliding particles arc at rest.
emitted in the direction of motion of the
on the a\'erage, before annihilating, if it of muonium. 9.9 What is the threshold kinetic energy positroll and the other in the OJlllOSite
i~ in (a) the singlet state, (b) the triplet 9.3 A negative pion may be c~tured into of the incoming particle for the prDCe!lSCS direction, find their energies in the L-
state? a stable orbit around thc nucleus, 1'011- illustrated in Figs. 9-10 and 9-1I? frame.

4'18 f.'undammlfll parlicks
0,16 The annihilation probability per unit
time of po~itronsis).. _ 7.4S X 10 -I~ns-l,
where It is the number of electrons per uni t
volume. Show that the h~f-life of positrons
moving through argon (Z - IS) is T -
2.67 X 1O-1 /p, where p is the pressure,
in atmos[Ihercs, of argoll.
9.17 Protons may be &ecelerated to an
energy of 33 GeV in the Brookhaven alter-
nating-gradiellt sYlichrotron (AGS). (a)
What energy is available for reactions
with the protons (at rest ill thc [...frame)
in Ilrookhaven's hydrogen bubble cham-
ber? (b) What energy is available if the
IIrolons are stored in a circular ring and
I1re allo"'ed to react with a ring of sooTed
l)ro10119 of the same energy which arc cir-
culating in the opposito direction?
O.IS A 100-:\1eV "II"-mcson deeay~, pro-
ducing a I'-meson emitted ill the forward
direction. Calculate the killetic energy of
the ,,meson in the I.... frame.
0.10 CAleull1te the energy of the photon
emitted II'hen a :!;O_particle, at rest in the
IArame, decays oo a hO_particle.
{).20 By application of the Lorentz trans-
formation for cnergy alld momelltum
(ApIlCndix I , Eq. ,\.16), obtain Eqs. (9.14),
"'hich relate the enl'rgy and momentum of
the photons in the C- and ["'framCl!. (Take
the X-axis parallel to the relative velocity
II'hieh is given by Eq. {).t2).
9.21 Considering the process .,..- + p+--
AII + KII, (a) II'hat are the pOl!sihle values of
<f for the two rcacting particles and for
the two resulting particlei? Determine the
value of <f for consenation of isotopic spin.
Also determine whether <f. and S are con-
served. (h) Repca~ the analysis for the
t)rOCCSII .,..- + p+ __ All + ... 11 snd conclude
if the process is expected to occur in nature.
9.22 Considcr the process p+ + p+-
p+ + n + ,..+. Dctcrmine. the total iso-
tOllie spin; arc '1". and ~tral\genegs COIl-
served? Repeat for p++p+->p++
n + e+ + ~.. This proeeM oecurs with a
much lower probability thsll the first-
mentioned procCSII. Why?
9.23 Check t.he several coneervation la~'s
(except energy, momentum, and angular
momentum) in the following strong inter-
action proce!lSCl!.
(a) P++P+-+j)++hO+ K +
+
(b) ... - 1'+ -- 2;0+ KO
(c) p++p+ ...... :::O +p++ Ko + K+
(d) AO + p+ ...... n+ p+ + "]Zo
(e) "]Z-+p+ ..... K ++:::-
Detcrmine in each case the values of 'To,
'1", and S for the reacting lind r-esultillg
particles.
0.24 Which COllservation la\\'S arc satisfied
and which are violated in processCl!
and ... 0 ......
Why is it that 2;0 __ A0 + l' ooeurs, but
l: + -> p+ + l' is not observed? Why is it
that :::- -+ A1) + ... - ooeurs, but :::- ......
",,0 + ... - is not observed?
0.25 Analyze the process 'j{- + p+ .....
0 -+ K+ + KO from the point of vic'"
of the conservation Ill"'!. Calculate the
thTC8hold kinetic energy of the "R--
particlc,
9.26 Show that the proccsses .,..- p+ .....
n +1', .,..-+ d -+ 2n +"Y, and .,..++ d .....
21)+ all imply that tho 811in of the pion is
eithcr 0 or I. (Sec the following problem.)
9.27 Let WI designate by v, the eross sec-
tion for the process p+ + p+ ..... .,..+ d
and by "2 the eroS'! section for thc inverse
process .,..+ + d -+ p+ p+.+ We can
show that the crO!!ll sections are related by
where p. and pp lire the momentum of th,c
incoming pion or proton in the C-frame of
reference and t. is the spin of the pion.
It has been found experimentally t.hat
", _ O.IS mb for protons with an energy
of 340 l\leV in the I.A rame and V2 - 3.1 mb
for pions with an energy of 29 MeV in the
[...frame. Verify that thCl!C experimental
rC!lults arc con~istent with f . - 0 but not
with _ I. Illi01l: In finding P. and pp
in the C-framc, Ilonrelativistie formul!lS arc
used Once the kinetic energies arc com"
puted.] Also, oo justify using the above
relation betll'ccn VI and V2, verify that the
total cnergiC!l in theCframe are COml)arable.
9.28 Using the law of COlI!Crvation of an-
gular momen tum, show that, in the decay
+
A -> .,..- 1)+, the resultant orbitalangu-
la.r momentum of the products in the C-
frame must be either zero (a-channel) or I
(p-channcl). As a rCl!ult, it can be shown
that the angular d istribution of the pions
+
is pro])Ortional to 1 k COil 1/1, where r; is
the anglo bctwccn the direction of motion
of the I)ion (in the C-framc) and the spin
-,+ 1'1 of the A o_particlc. Verify that this angular
di.~tribution is incompatible with the con-
scrvation of parity. The experimcntal
value or k is 0.62. (llint: To prove the last
part, make a reflcetion in a 1)lane perpen
dicular to the spin of the A O_particle.]
9.29 Show that ""o-de<:ay violates the COIl-
servation of isotopic spin. Which interac-
t ion could be resl)Onsible for the l)rOC<!SS?
9.30 Let us designlHe the isotopic spin
wave function of a nucleon corresponding
+ to 1" . - :l:t by ~ (), so that ~(+) carre-
sl)Onds to a proton and H-) to 11 neutron.
By !imilarity with the spin wa\"{' function
of two l)articlcs (Section 4.2), write the
isotopic spin wave functions of two nu
+ clcon~ eorreSl)Onding to 'T - 0 and 'T - J.
In each Cl!.$e indicate the value of <f.
Identify the particles involved in each
wave function.
9.31 Gil'cn that 'il i~ the distaliCc be-
twccn particles i and j, show that j(r,j)
is trsn~lationslly invariant. Determine
whether the gravitational and electric in-
ter&etions are translationally invariant or
not.
9.32 l\lllkc !l. table showing the relation
of the strong, clectromagnetic, and weak
interactiOll1l oo the following conscr\'ation
laws: isotopic 81)in, st rangenC;S.~, parity,
charge conjugation, snd time reversal.
9.33 11011' are electric and luagnctic fields
affceted by time rcversal? Sholl' that
Prohltml ,,.
Maxwcll's equations are invariant with
respect to time rcversal.
9.33 Show that rcfleetion on the X r-
plane (or any other coordinate plane)
changes a right-handed frsme into II leh-
handed frame.
9.35 Show that if ,I and IJ are polar \'ee-
tors, then , I )( B is an axial vector, and
that if A is ])Olsr and n is axilllihell'" )( U
is r)Olar. (llinl: Analyze the behavior of
11)( IJ lll)On reflection on the XI'-pJnne.j
9.36 Write the rectangular coml)Onents of
L and analyze lhe way th<'y change for
reftcetiou on the X1'-plane. Compare with
the discussion collcerning Fig. 9-16.
9.37 Discuss the behavior of :\Iaxwell's
equations in regard to reflection on the
X1-plal1e. Do you conclude that these
equations are compatible with conJl(!rva-
tion of parity in electromagnetic inter-
&etions?
9.38 Sholl' thal a reflection at th e origin
of coordina.te~ (i.e., the change of x, 1/, t
inlo - x - !I, -z) is equh'alent to a re-
flection on thc Xr-plal1e, followed by a
l80" rotation around the ZIL.~ i~. Con-
clude, thcn , that. the parity behavior lI'ilh
regard to reflection in a plnue and a l)Oint
arc the sallie.
9.39 It can be shown that, in electric
dipole transit ions, the electromagnetic
field of the photon has odd parity. Show
that thl' flC lectioll rule tJ.1 ,. 0, introduced
in Section 3.4, is requirefl if parity i~ con-
served in the transition, or, in a more gcn-
eral form, that the initial and final states
must ha\'e Ol)posite Ilarilies.
9.40 E~t imate the areas undcr the cun'es
8ho\\'n in Fig. 9-31 and compare with the
charge of a proton find a neutron.
9.41 It has been observcU that 152u
decays by electron capture according to
152E\I +e- __ l~2Sm+~. In turn, the
excited samarium decays by gamma emis-
sion according to IS2S m __ U2S m 1'. +
Both u2Eu and IUS m nuclei have zero
spin . By obscn'ing the 1'-raya emitted in
 ..
430 fUTldamtfl{o{ par/idtl PART 2
d irection oppogite to that of emission of
Ito
the neutrinos, physiciat.s found that the
,>'
STATISTICAL PHYSICS
photons arc predominantly right,.hllnded
polarised (that is, they have negative
helicity). Show that this impliet that the
neutrino al!lO hIlS negative heJicity. 11/int:
Analyac the eOllacrvation of angular mo-
mentum for the overall process.)
9.42 In the process FiS lire 9-37 ..

predominantly lIS shown in the figure. Is

the Ao's are strongly polarised, with the ir
spins perpendicular to the plane of produc-
tion in the di rection of the vector p . X PA
(sec Fig. 9-37). Is parity conserved in the
procc!lll? In the sub!lCquent decay of AO
inw '11" - and p+, the producw arc emitUld
parity conserved in the A-deeay procC!l!l?
{Compare with Problem 9.28.)
9.43 Show that if, in the 6<lCo experiment.
(Fig. 9-18), the electron!! were emitted
with the same inUlnsity in the forward and
backward directions, parity would be con-
served in the proce!lll.

10 Classical Statistical Mechanics

11 Thermodynamics
12 Thermal Properties oj Gases
13 Quantum S tatistics

...
 -
10
In the preceding chapters of this text we have studied the fundamental constit-
uents of matter: particles, nuclei, atoms, and molecules. But we cannot see or
CLASSICAL STATISTICAL
feel individual atoms or molecules at work. Rather we observe the result) of a
large number of them acting in a more or less organized manner; i.e., macroscopic
MECHANICS
processes. The properties of mlltter in bulk (called macroscopic properties), lIS we
ordinarily observe them, are the result of these collective actions. The collective
behavior of large numbers of atoms and molecules is basically a result. of thcir
electromagnetic iutcmelion, since gravitational interaction plays only a minor
role and the strong and weak interactions affect only nuclear processes. Familiar
processes, such as melting and vaporizatioli, diffusion, thermal and electrical con-
duction, emission of electrons by hot metals, aud many others, as well as such
concepts as tempemture, heat capn.city, heat of change of I)hase, etc., fall in this
category of collective properties. 1t is the understanding and control of these
collective phenomcna that primarily interest the applied physicist, the enginecr,
the chemist, and other scientists in their endeavor to usc the forces of nature for
the welfare of man.
To desc ribe processes involving 1\ very Inrge number of particles, special methods
must be devised. Thesc methods are, by necessity, of a statistical nature, since
we cannot take the detailed motion of individual particlcs into account (nor is it
necessary to make such an effort to obt-ain results of practical value). For this
rcason the discussion of macroscopic processcs from the molecular point of view
constitutes what is called 8lalia/ical phY8ic8. Thc word Ustatistical" must be inter-
preted as al)plying to a techni<lue fo r describing processes involving laTgC numbers
of particles whose individual interactions are known, without considering the in-
dividual behavior of each particle. In this respect, statistical methods have been
applied to the discussion of many-electron atoms and many-nucleon nuclei.
In this part of the tex~ we shall first develop the statistical method known as
da.5Mrol Ilaliatica/. mechallic8, discuss its general applications to what is called
lJiermodynamiCB, and apply the method to analyze the properties of gases. We
shall conclude this part with a brief introduction to quantum 8tJJI.illica/. mMalliu, 10.1 Jntroducl ion
illustrating some of iis applications.
10.2 Stalislical EqlLilibriulIl
10.3 The Maxwefl-Boll:lIlann Distribulion Law
10.4 Temperature
10 ..5 Thermal EqlLifibriulIl
10.6 Application fo lhe Ideal Gas
,

...

434 Cl(l. uiwi rlalilliroi nmhanur (10.2
10.1 Intrtnl"ctltm
~ [ cchaniCllis foundcd on certain gcncral principles, such M the conservatioll of
energy and momentum, that are applica~le to the motion of intcracting particlcs.
In this chapter we shall extend the principles of I)lechanics to systcms of many
pnrticlcs, emphasizing the methods used to obtain collective or macroscopic prop-
erties of the system, without considering lhe dctailed motion of each particle. This
technique is called 3lalislical mechamCIS. W~ use "particle- hero in a broad sense,
meaning a fundamental particle, such M an electron, or an aggregate of funda
mental particles, such as an atom or molecule. Thus a u l)ftrticle~ will be each of
the well-defi ned and stable units composing a given physical system.
T he fact that we need a statistical approach when we nrc dealing wilh the
macroscopic properties of matter is eMily recognized when we note that in one
cubic centimeter of a gas at STP there nrc about 3 X lO"' molecules. It is not
only practically impossiblc, but also unneccssnry to take into account the motions
of each of these molecules in detail to determine the bulk properties of the gas,
such as its pressure or temperature. On the other hand, to make a statistical
iUlalysis of a manYI>article system, wc havc to make some reasonable estimate
nbo ut the dynamical state of each particle based on the gencral properties of the
particles . We mnke this estimnte by introducing the concept of the prOOability of
di81ribulion of the particles aillong the dilTerent dynamical stales in which they
Illay be fOWld.. When we introduce the idea of probability, this does not imply
that we assume that the particles move randomly or in a chaotic way, without
obeying any wcll-defined laws. The concept of probability arises from our method
of estimating the dynamical statC8 of the particles in a syswm, not from the
mechanism by which, na a result of thei r inWrn.ctions, the particles of a system
are distributed in nature among the possible dynamical slates. Hence the validity
of the statistical analysis of a many.p.'I.rticlc system is directly related to the va
lidity of our assum ptions concerning the probabilit.y distribution of the particles.
10.2 S ,atls tie ol Equilibrium
Consider an isolated system composed of a large number N of particles, in which
each particle hna available to it several statcs with energies E" 8 2 , E 3 , ... . T he
encrgy states may be quantized (as are the rotational and vi brational stales in a
molecule) or they may form a practically continuous spectrum (as for the trans--
lational kinetic energy of the molecules in a gas). At a particular time t he par.
ticles are distributed among the dilTerent states, so that rtl particles have energy
E,; n2 particles hnve energy E 2 ; and so on . T he total number of p.'I.rticlcs is
n, +n2+ "3+ . =
N=
,
L: n;, (10.1)
and we flSSlIllle that it remains constant fo r all processes occurring in the system .
The total energy of the system is
U = nlEI + n2E2 + n3Ea + .... = L: niE;. (10.2)
10.2) 435
1'his cxprcssioll for the total energy of thc system im l>liciUy flSSumes that t he
particles are nonintcracting (or thllt thcy interact only slightly), so tlmt to each
particle we call attributc an cncrgy dc]>ending only on the coordinates of the
particle. If we eonsidcr internctions, we must udd to Eq. ( 10.2) terms of the form
E,,12 + E p13 + . ... + E p 23 + .... corresponding to the potential energy of inter
action betwecn pairs of particles. Ench term includes the coordinates of both
interacting particles. In such Il case we cllllnoL speak of the energy of cach particle,
but only of the system.
It mny sccm at first sight that ou r discussion is thcrefore unrealistic, since all
particles that make up physical systems are interacting. However, under sl)Ccial
conditions we can use a teehnique called the uif-collsisleni field, in which each
particle is considered subjecl. to the (U~raye interaction of the othcrs, with an
average potential encrgy which depends only on its coordinates, so thnt we can
still write U as in Eq. (10.2), but now B,' :cI Hi( + E pi .w. For caseS ill which
the interactions among the partieles must be considered explicitly, other tech
niques musl. be used. Wc shnll diseuss these in Chapter 12 in cOllnection with
real gases .
If thc system is isolated, the total energy U must l>e constant . However, as a
result of thei r mutual interactions and collisions, the distribution of thc I>artieles
among the nvaihl.ble cnergy stales may be chtUlging . For example, in a gas a fast
llIoleculc may collide with !l s:low one; after thc collision the fast molecule may
hnve slowed dowlI and the slow one may ha\"e spcd up. Or an excited atom ma~'
collide inelastically with anothcr atom, with a transfer of its excitation energy into
kinetic cnergy of both atoms. Hcnce, in both eX:lmples, the particles after the
collision {lrc in differentlStates . In other words, the numbers Ill, 1/2, n3,"" which
give thc pll1"tilion (or distribution) of the N particles among the nvnilable cnergy
slntes, may be changing . It. is reasonable to nssume that for each macroscopic
state of n system of particlcs thero is a parlitioll which is more fa\'orcd than any
other . In other words, we llIay s..'I.y that, gire" tile physical conditionll of iJle lIy31e"l
of particlell (that is, the number of particlcs, the total encrgy , and the structure
of ench particle), there ill a mIMI wobabie pa rI it ion. When this partition i$ nchieved,
thc systcm is said to be in 8lalislical equilibliulII.
A system in statistical C(luilibrium will not depnrl from the nlOsL prob:lble par
tition (cxcept for statistical fluctuation s) unlCAA it is disturbed by un external
a.ction. Dy this we mcun thnt. lhe IXlrtition numbel"l! lit, 11:, flJ, .. .. lIIay fluctuate
around thc values corresponding to the most probable p.arlition without no--
tiecable (or observable) macroscopie effects. For e)(tllllple, suppose that we havc II
gas in statistic...'1l equilibriUlll , in which a molecule of cnergy H, collides \Iith a
molecule of encrgy EJ ; after thc collisions their energies nre E', and R... We Illay
flSSUlIIC thnt within l\ short tillle another pnir of molecules is removed fronl cuergy
states 1',', and E. and the samc or another puir of molecules is moved into energy
states H, nnd Ej, so that , sttltisticully, the p:lrtilion has not changro.
Thc key problem of statistical mechanies is to find thc Illost probable pnrtilion
(or distribution law) of nn isolated system, given its composition. Oncc the most
probnble pnrtition has been found, the next problem is to devise methods for dc

43' CllU,icoi ,/olilticai mtchaniCl (10.3
d ying the macroscopically observed properties from it. To obtain the distri bution
law, certain n&mrnptions are required. One may t ry severol plausible ass um ptions,
until a distribution law in accordance with experimental results is obtained.
Three distribution laws or stali>ltics are presen tly used. One is cn)led the Max wtll-
Boltzmann diSlribulion law, which is the basis of classical slalisliclf. We shall sWdy
i~ in this chapler.
Classical stnlislicai mcchaniCIJ 11'9.8 developed in the 1 !l8~ I)(l.rt of the nineteenth
century and the beginning of the twen tieth century as the result of the work of
Ludwig Boltzman n ( 18:14- 1006), James C. ;\ Iaxwcll (183 1- 1879), and Josiah W.
Gibbs (1839- 1003). Classical statistical mechanics has Il vcry broad applicabilit.y,
cS]>ccially to the discussion of many prol>crties of gases. The remaining two dis-
tribution laws, called Fermi- Dirac and BOIle-Eill steill, belong to qtwIllum 81alislics
and will be considered in Chal)tcr 13. Classicnl statistical mechanics can be con-
sidered as a limiting value of the two (Iuantum statistics (sec Section 13.9).
Let us consider a system composed of 11. large number of identical and distinguishable
I)articles. By identical I)!l.rlicles, we mean that the particles hnve the samc strue-.
lure and eomposition. By distinguisha ble Imrticles, we mean that we can dis-
tinguish, or tell the difference, between one ,mrticle and another identical I)article.
A t first sight it seems that the re is a contradiction between identical and distin-
guishable, o.nd indced this is the case! Lo.ter on we shall reconsider this appMent
lack of logic; however, t he results we shan obtain now are sufficiently sim ple to
justify a preliminary discussion of such a system.
.,--------<---___________ n'_2
f<:, --_______ ___ ___ ~, - ~
'.----------.---------- 114-I
Fig, 1 ~ 1. Distribution of particles
among different energy states.
, .
,, --------_ ___ _______ n,_2
.
t'2 ----------___________ n'_O
'0 -------_,._<-_______
, , "1_ 3
Let us re present a particular partition nlt 112, 113, .. by the geometrical arrange-
ment shown in Fig. 10-1. Each line represents 1l. particular state of ene rgy B j , and
the number of dots indicates the number 1Ij of particles in each energy slate. III
our example 111 = 3, n2 = 0, 113 = 2, 11 4 = I, etc,
Our first assump tion is that all energy stntes are equally aceessible to the par-
ticles of the system; i.e., llial all energy l /{Jies h a ~ the lame probobility oj being
10.3) The MacIU1l-BoII:mIl1lll distribulion Ill w
rxcupied. Then we shill! \SSUllle that
the probabilily oj a particular paTtitjtm j, 1"OIJOrlionai. to the number oj
different U"ayl ill which the parliclu call be diatributed among Ihe QL'ail
able energy Illatell /o produce tlie partitioll .
Let us then see, as an example, the numbe r of different w:\ys in which the partition
of f ig. 10- 1 can be obtained. By different lI"e mean that the numbers '!It 112, n3,' ..
are fixed , but the particles in each st:lte arc different. That is, a partition in which
particle a is in state EI and I)'"lrticle p is in state E3 is considered different from a
partition in which particle a is in state Ea and particle p is in stale B I , This is a
consequence of l\.SSullling that the component particles arc distinguisha ble. If
they were indistinguishable, we would have to l\.SSume that the two partitions
were the same.
To start fi lling the state E I, we may select the first particle from anyone of the
N particles available. Then there are N distinguishable W:lYS of selecting the first
particle. The second pllrticle C:ln be selected in N - I different ways, si nce only
N - I ptlrticles are left aVll.ilable. And the third particle can be selected in N - 2
different ways. So the total number of different distinguishable ways in which we
may sclect the (irst three particles to place in statc EI is
N1
I N(N - I)(N - 2) ~ (N . 3)' ( 10.3)
Let us dcsignlltc the th ree chosen particles by a, b, and c. We llIay pick them in
any of 1hc 31 = {; different orders or permutations abc, bea, cab, bac, acb, coo.
But thcsc 3! different orders of placing Imrticles a, b, I\nd c in E, give the lame
partition, since they all c<>rrespond to particles a, b, and c, in state E I A partition
is determined only by the number and labeling of particles in each slate and not
by the order in which they were placed there, which is immaterial once the parti-
tion is arranged. T herefore, to obtain the tOlal llumber of distinguishable different
ways in which we lIlay select. the first three particles in state E" we must divide
Eq. (10.3) by 3!, resulting in
N!
3!(N 3) 1
The geneml expression for the total number of distinguishablc different ways of
placing 11 L particles in stale E 1 is then
( lOA )
This is just the number of permutations of N obj~ts, takcn 111 at a time. When we
pass to the second state E 2 , only N - 111 particles are available. So if ,,e want to
place 112 particles in state E 2 , we must usc Eq. (lOA) with N replaced by N - nl
 -
10.3)
'"
(lnd Ttl
ClfUliro/lfa/i,lical muhalliel

replaced by 112, resulting in

(10.3 Tht Mruwell-Boi/:mrll/fl dis/ribuliOlI law

Finally let us remove the condition of distinguishability. If 111\ I>articles are

idenlical and il!distinguishable, one cannot recognize the dilTerence if, for exam ple,
( 10.5) in the partition in Fig. 10- 1 I>articlcs a and p exchange 1>laccs. Therefore all N!
pern~ations among the particles occupying the dilTcrent states give the S:Ulle
partit ion. That means t hat. \\'e h:wc to divide Eq. ( 10.7) by N!, resulting ill
For the third state we have only N - 11 1 - 112 particles left, Ilnd we arc placing
particles in it, 80 that instead of Eq. ( lOA) we get
113

(10.8)
(N nl 112)!

The process call be continued until all energy states have been considered . The
total nu mber of dis tinguishable d ifferent ways of obtaining the I>tlrtition 11 L, 112, "3,
... is obtained by multiplying expressions (lOA), (10.5), and the successive ex-
pressions for nil remaining energy states. I n doing this the student may note that
a !lumber or factors, such Il.S (N - nl) !' (N - 111 - 1I2)! etc., cancel Ollt, resul ting
in the sim plified expression
This is the expression for the probability of :1 distribution ill Maxwell- Boltzmann
statistics.
We can obtain the equilibrium state, eorresl>onding to the most probablc par-
tition, by finding the ~inlum of P (givcII by Eq. 10.8) oompatible with condi-
tions ( 10. 1) and ( 10.2), with Nand U as constants. ,,' he method is a straight.-
forll' nrd mathematical techniquc, and is cxplained in detail in Example 10.1. The
result is that the partition having maximum I)robability is given by

(10.9)
(10.6)
where a and fj are tll"O parameters which, as will be ShOWII, nrc rclated to the
which gives the num ber of different distinguishable ways in which the partition physical prope rties of the system. The {IUnnliLy (X !nny be cxpressed in terms of
'tJ, 11~, 1la, ... can be obtained. We shall now assume that the probabi l :~y of lhc total number of partielc, N. Using Eq. ( 10.9), wc have that
obtaining tha~ partition is proportional to P. For example, for the partition of
F ig. 10- 1, the probability P is N = nl+ 112 + 113 + ...
= {Jle--flE, + (l2e-a-~H. + .
P N!
... 3!0!2 H !41 .. = e-({J1e-BE, + O-:e- flE + g3e~' + ... )

We Illust take 01 equal to I, since ni = 0 ean be chosen in only olle way. T he

= e-Q (~9.'t-flEi) = e-<!Z,
numbcrs7l1' 712, 713,'" in Eq. (10.6) must be chosen in sueh a way that Eqs. ( 10. 1) where
a nd (10.2), which give the total number of par ticles and the total energy, are
satisfied. Z = L...J g,'I: -~1.'; .
"" (10.10)
So far we have llSS umed that all availa ble s~tes have the same probability of
being occupied. I t may happen that the states have different inlrin,ic probabililie8 The quantity Z, called thc porlilioll fum.:l;ol!, is a very important expression which
g,.. For example, a oortain energy state may be compatible \\'ith more different apIX'MS quite often in many cnlculations. We lIlay thus II rite f)-a = N j Z, and
angula r mome ntu m states than other states, and therefore is more likely to be Eq. ( 10.9) becomes
occupied. When this intrinsic probability is taken into account, the probability
P of a given partition is slightly different. from Eq. (lO.G). Obviously, if gi is the N . -61.',
prob..'lbility of find ing a particle ill the level of e nergy E" the probability of finding
Iii = -ZY,c . (10.11)
1.11'0 particles in lhat level is g,' X gi = g~, and for IIi particles it is gi X gi X Oi X
X gj = !J~i. Thus the total pro bability of a given partition , instead of being Exprcssion (1O.11) constitlLtes the M nXlt"eIl-I1Qllzmal!lI (lis/ribillion law. T he qunn-
given by Eq. ( IO.G), is given by tity fj is rclated ,to the energy of the system, or more pred.'!!e!y, to thc avcragc
cncrgy of a particle, as will be explained in Section lOA.
We "hall noll' illustrate all npplic:Hiun of Eq. (IO.l l ). From the definition of
( 10.1) average I'nlue, we have lhal the :Ivcfflge vulue (for a gh'ell partition) of a physical


(10.3 T he Mazwdl- BolI:malln dil/ribll /ion faw 4'11

436 /0.3)
c)[presscd as n function of the particle energy E' is givell or, using Eq. (10.1 ), we may write

In P .,. 11' - L
, lljlnn.!f};.
. (10.1 3)

Differentiating th is expreS!!ion (rememix"ring that j\' i~ constant and tllll$ dN - 0),

.<l most probnble or cCluilibrium partition we ha\'c, usin~ Eq. (10.11),
we obtain
d(ln P ) - - L, (dn;) In n J {/; - L,
nld{ln ,.;f{/;)
P..... """ ZI "L.J " (E' ) 4,-
, (I. e . .. j
(10.12)

For cx:ullplc, if the piLrticlcs of a system can be in only two stllles of energy,
- L (dnj) In n ;f{/; - L 1l,{dll ;)/1I 1
8 1 = +i and 8 2 = - f , both with the same probability (Il l = 112 = 1), thell
- L (dll;) In n ll{/i - L dll ,. (I0.H)
Z = t-~K, + c-/l t:, = t-/l + t/' = 2 cosh Pt ,
But from Eq. (10.1), since dN - 0 becall:;t II' is con~ tant , we have
and the Ilvcmgc energy of a particle i,;
(10.15)
1 (E' -,If:,
E".".-= :2 "'It
+ E' 2,-{lE,)
Therefore Eq. (l 0.1 1) redllces to
u -(l , - E/'
t:mh fj{,
2 cosh p e
- t
- d(ln P) - L (In n ;l{/;) d>l l - 0, (10.16)

The to tal energy is

We writt !cro on the right side of Eq. (10 . 16) beclluse 11'0 are looking for the equilibrium
U "", NE'.,_. = - Nt tanh PE, slale for wh ich P i.s milximum, or dl' - 0, and th<'rrfore d(!n P) _ p-I dP - O. If all
Ihe chang~ dnL, dnz, dlla, .. were arbitrary, we could 8ati~ry E<I. ( 10.16) by making
which allows us to find fj in terms of U.
III nl / gl - 0, In 112/ {/2 - 0, In 113/ 1/3 - 0, ... or 111 - gl, 112 - (12 ,

f.' XAMPL. 10.1. Ikd\'at ion of the nlOS L probable or equilibrium part ition. HOII'ever, the ch8lJges dl1, are not entirely arbitrary betau.e of condition (I0.15), "hieh.
Solutio" , The mOS L probable or equil ibrium pllrtition corresponds ( by defin it ion) to deri\ed from the ('Onstanc), in thc number of particles, and a ~imilar condition,
11'113

the maximum of P. Thkl maximum, in lurn, corresponds to the situation in wh ich the
L E;dn. - 0, (lO.lj)
change of P is ])ractically U'ro (dP - 0) for small changes dnl, dn2, dn3, ' .. in t he occu-
pation numb('111 nit 11.2, 11.2, ... Howe\'er, instead of obtaining the maximum of P, it is
easier mathematically to obtain the maximum of In P, ,,hieh corresponds to t he !amc resulting from the constancy of thc internal encrg)' and obtaincd by differentiating
value of P. Now, from Eq. ( IO ~), we have Eq. ( 10.2) and setting dU - O.
To compensate for the two cond itions ( 10.15) and ( 10,17), II'C introduce tll'O arbitrary
InP _ l\ l lngl +1\2 In~ +n3 ~h+' " pa.rameters a and fl, called "Me/ermined m"lIipliefl, accordillg to a mathematical tcth-
- In I\I! - In 1\2! - In na! - . . . Ilique suggested by Lagrange (see Appendix VI I). Multil)lying Eq. (10.15) by a,
Eq. ( \0.1 7) byfJ, Ilnd adding lhe~e to Eq. ( 10.16), we obtain
Using Stirling's fo rmula for the logarithm of the fat toriill of a very largt number (see
Appendix V), L (In II J I} ;+ a + fJE;) dnl - O.
Inx ! ... xln:t - x,
This adds tll'O new arbitmry coefIic icHt.I! a an d fJ to comrlCnsate for the two restricth'e
and assuming that Ill, 1l2, r13, . . . are large numbers (since physical syswms IIrc in gcn cond itions ( 10.15) and (1 0, 17). T he equilibrium distribution is then obuined if
era l composed of a great mll ny particles), we have
In nJ g,+a +fJ Ei - a
In P _ ll l lllgl + ~ln~ + n3In"+' "
- (nllnlll - Il.) - (1l21n1l2 - 1l2) - (Ilaln lla - 113) - .
- - Ill In III/gl - 1l21n f\Z/g2 - ... + (Ill + 1l2 + " .) , which i8 the result pre\'iou~ly stslrd in Eq, ( 10.9).

...
 -
(1 0.3 10.f4) T~mpl!rallU"e 4~3
436

<:Imposed of 4000 particles which may be in one of three Canceling thc common factor t in the !SeCOnd rela tion, we ba,c
..ced, whose energies are 0, f, and 2f, all hav ing the same
.g. 10-2). This system, for example, could consist of atoms
'I1(l +;t: + %2) _ 4000,

. tnll.lm is equal to I, placed in a magnetic field . Compare the 111(;1: + 2.1:~) .. 2300.
vf the partit ion in which there n.re 2000 particles in the lower level,
.,e level, and 300 in the upper level wi th the pn.rlition resulting fro m the Elimi nat ing 1110 wc ob ta in an equll.lion For;l::
_,e pa rticle from the middle level to the lower levelaud allother to the upper
.... roeess compatible wit h the conservation of energy . 47z~ + 1h - 23 - 0,

E, .. ~.,------------ " or z - 0.5034. (Only the positive root is used. Why?) T he refore III .. 22i7 (the figure

Fig. 10-2. Syslem

energy le\cl~.
wilh three
1':2'" - - - - -- - - - - --

/0;1_ 0 - -- - - --
.,

- - -- - .,
p - , .-
has hccn roun dcd), Accordingly, 112 _ 1146 and 113 _ 577. The col"l'C!lponding part ition
probability is

2277!1 J461517!

Le t us no \\' compute the change in P whcn two particles are removcd from the inter-
Solu t iQn, According to Eq. (10.8), the Ilrobabilitie!! for the firs t !llld ~ccond partitions arc mediAte le"el and transferred to the uPI)('r and lower le" cls. T he new part ition pro b-
ability is
_
,''''' g~ OOO

P' _ fJ ""
P I .. 2OQOlliOO!3001 P2 2001 116!1S!30 I !
22781 1144!5781
Instead of co mputing the ,'ahl<'8 of PI and P 2 (which we could do by using I:~I ' 10.13), The ratio of the two probabilities is
we shal1 simply find thcir ratios:
P' 1146 X 1145 1,3 12.no
P2 .. liOO X 1600 _ 2.888.300 _ 4.8.
PI 2001 X 301 602,301
Ii - 2278 X 578 1,316,684 - 0.9966.

Thus the mcre tran~fer of two psrlicl<,s out of 4000 to other \c,'cis Challgl'5 the probability Therefore the two probabilities are essentially the same; th is is M it should be, since, if
P is a max imum, /lP must be zcro or vcry 51lls11 for a small change in t he distribution
by a factor of 4.8. This mcans that partitions PI and P2 sre both far from beillg the
nu mbers of an equilibrium partit ion.
equilibrium partitioll; this !ituation is duc to I1n excessive population of the middle Ic"e1.
Therefore t he system will try to e,'olve to a state in which the middle level is leM popu-
lilted. It is suggested th n. t the student repeAt the problem, considcring other llossiblc 10.4 T.m.pe.rntlfN!
distributions of particles, 11.11 cOlllpatible with the same lotal energy. (Shift two more
particles from the middle level or move one particle from the uppc r lcvel I1nd another '~ he paramete r (j of E qs. (10.10) and (10. 11 ) is directly related to
II. physical quan-
from the lo wer level into the middle level and recompute the relative probabilities.) ttty, t he temperature, which was origina1iy introduced more to describe a sen-
sorial expe rience t han a statistical I>roperty of an aggregate of pa rticles. We first
EXA,\fI'LE 10,3. Determine the most probable or equilibriulll partition for the system note that, if we are to have dime nsional consistency in Eqs. (10. 10) and (10,11 ),
of Example 10.2. wc must express (j in reci procal energy units; t hat is, J-I, eV-I, etc. Using
Sol .. /ion , The system is com]lOi!Cti of N _ 4000 ]larticles, and according to lhe data Eq. ( 10 .1 I), we have th at t he total energy of a system or particles in statistical
given in E1(amplc 10.2, ils lotal cnergy (bCC Fig. 10-2) is 2000 X 0 liOO X f 300 X + + equilibrium is
(2f) _ 230Ck Using Eq. (IO.!I) for the mo~l probable partition, wc must have, according
to the notation of Fig. 10-2, and with gl - U2 .. 113 '"' g, U = n lE I + n 2E 2 + 113B3 + ...
= t (VIE l e-ilK, + v28 2e- IIE + g3E3e~1I +.,.)

or, if we dcsignate e-/h by x, we have 112 - II!Z and 113 = 1I!;l:2. Thn~ conditions (10.1)
and (10.2), which gil'e the total number of particles and the total energy, re~Jlecll\'e1y, "
become (10.1 8)
111 + 1"1 IX + nl%2 _ 4000,


442 (10.3 10.4) T~m~raluu

EXAMPL"; 10.2. A system is com,lOSe<i of 4000 p:1rtieles which may he in one of three Canceling the common factor t in the second relation, we have
energy states or levels, equally spaccd, whose cncrgies are 0, f , and 2f, all having the Mme
intrinsic probability g (lICe Fig. 10-2). This system, for eXAmple, could consist of atoms ",(I + % + :r;2) _ 4000,
wh~ to tal angular momentum is equal to I, placed in a magnetic field. Compare the n,{x + 2L2) _ 2300.
relative probabilities of the partition in which there are 2000 particles in the lower lel'el,
1700 in the middle lel'el, and 300 in the upper le\'el with the partition resulting from the Eliminating nl , we obla.ill an equatioll for r:
transfer of one l>article from thc middle le\'el to the lower le\'el and another to the uPIJoCr
level, a process compatible with the conservation of energy. 47:r;2 + 17% - 23 - 0,

or.z: - 0.5034. (Duly the positive root ig used. Why?) Thcrdore nl _ 22i7 (the figure
has been rounded). Accordingly, n2 _ 1146 and n3 _ 577. The corresponding pattition
- - - - - - - - - - ". proba.bility jg
Fig, 10-2, Systelll
energy levels.
Ilith three ,'"
p - "'..:[-,"'=~
2277!1146!577!
8 1-0 - - - - - - - - - - - - ",

Let Ug now compute the ehange in P when two particles are removed from the inter-
Solu ,ioll: Accordillg to Eq. (10.8), the probabilities for the first and SC'c6nd partitions arc media.te level and transferred to thc uPlJCr and lower levels. The new partition prob-
abili ty is
.~ <000
I> _ IJ . 4000
p - g P' _ IJ
I 2000! 1700!300! 2 200I!lU98!301!
2278!1I441578! .
Instead of computing the "alul's of PI and P 2 (which we could do by using Eq. 10.13),
we shall simply find their ratios: The ratio of thc two probabilitie8 is

1>2 _ 1700 X 1600 _ 2.888,300 _ 48 P' 1146 X 1145 1,312,1 70

PI 2001 X 301 602,301 .. P - 2278 X 578 1,316,684 - 0,0066.

Thus thc merc trllilsfer of t"o Jlarticles out of 4000 to other ICI'el, changes the probability
by a factor of 4.8. This means that partitions P, 9.IId P2 are both far from being Ihe
equilibrium l>artition; this situation is due to an excessive population of the middle level.
Therefore thc II)" tem will try to el'oll'e to a state in which the middle lel'cI is legs JlOpu-
lated. It is suggested that the studen t repeat the problem, considering other 1)()!\Sible
distributions of partic~, all conlp3tih1e with the ~ame total energy. (S hift t"o more
I)artieies from the middle level or mO\'e one particle from the upper le"el and another
from the \O"'er le"cl into the middle Iel'el and recompute the relative probabilities.)
EXAM I'''''; 10,3. Dctermine the mOst probable or equilibrium partition for the s)"~tem
of Example 10.2.
Solrllior, : The s}"~tem i~ compo~ed of N - 4000 particlcs~ and according to the data
gil'cn in E. xample 10.2, iL~ total ('Ilergy (~ce Fig, 10-2) is 2000 X 0 + 1700 X t + 300 X
(2f) _ 2300f. U~ing Eq. ( 10.9) for thc most probable partition, we Imht havc, accord ing
to the notation of Fig. 10-2, and with IJI - !J2 - 113 - IJ,
or, if we designate by or, we lu\\"c nz - /lIZ aud 113 ~ 111.1"2. TIIII,; eouditiOIl~ (10.1)
t- I ,
and (10.2) , which give the loilll number of particles llnd the total enl'rgy, respectively,
becomc
Thercfore t he t\\'O probabililiC!l arc Cl!Sentially the same; this is as it should be since if
P is a maximum, tlP must be zero or very ~ mall for a ~mall change in the dis'tribution
numbers of an equilibrium partilion.
10.4 T e nrpe.rature
~he parameter fJ of Eqs. ( 10.10) and (10. 11 ) is diro<:t!y related to a physical quan-
tity, the temperature, which was originally introduced more to desc ribe a sen-
soria! experience than a statistical property of an aggregate of particles. We first
note that, if we nre to have dimensional consistency in Eqs. (10.10) and (10.11),
I\'C must express. (J ill reciprocal energy units; that is, J - I, eV-', etc. Using
E q. (10.1\), we have that the total energy of a systcm of particles in statistical
equilibrium is
U = nlE, + n~E'2 + naEa + , ..
= ~ (gIE,e-fJK , + [/2B2e-~#' + g3E' ae -lJ., + ...)
(10. 18)
 (10.1,
-
Clallical J/ali.rlicol mechanic,
10.4) Ttmpera/IIFt 41,5
Using the definition (10.10) of the p:\rtitioll fU!letion, we may write U in the
alternative form f3
equilibrium. The reason for this is that the parameter appears oilly in connection
with the calculation of the most probable partition of a system, which eorrespolld.'j,
U = - i :f3(~9'1!-IIE{) = - ~ ~! = -N :f3(lIlZ), (10.19)
by definition, to the equilibrium state. If the system is 1I0t in equilibrium, we
may s~il1 speak of an "effective" temperature of each small portion of the system,
assullung that. each small I>ortion is almost in equilibrium.
which is all iml>ortant rebtion betwccn the total energy and the partition function Whcn we introduce the dcfi nition (1O.2J) of temperature in Eq. (10.10) we
of a system in statistic!!l C<luilibrimn._ The average energy of a particle iii may write the cquilibrium partition fUllction as '

8m = ~= - :fJ (In Z). (10.20) (lO.22)

Xote that, given a physical system described by the g,'s and the E,'s, the partition Similarly, the equilibrium OCcullMion numbers arc given by
function Z (and hence the total energy U) as well :18 the average encrgy of a par
ticlc, 6'.v~, are fUlietions of {J (and also other parameters which determine the n ,. = N, ,~;!.T
Z' , (10.23)
maCTOSCOI)ic state, such as volume and preSiiure). That is, we may use the pariull
f3
cter to characterize the inlenml energy of the system. However, it has been \\:hich gives the ~IflXwellBoltztllann distribution law in tcrms of the temrlCrature.
found more convenient to introduce a new physical quantity instead of {J. This Smce {J = I / kT, then dfj = - d7'/ k1'2, and we CMl write Eq. (10.19) as
quantity is called the absolute temperatw'e of the system; it is designated by 1', and
defin&! according 10 the relation d
U = kNT2 dT (In Z). (J0.24)

k7' = !.. (10.21) T he average energy pcr particle, UIN, is given by

~

The qualliity 1.:1' LIlust obviously be exprcsscd in units of energy, such as joules
or electron volts. Thc cOl\stnnt k is called the Bol/zman!! conS/OIlt. its value is
determined after the units for l' arc chosen. It remains to be shown that the
tempemture we hnve definc<1 here coincides with the temperature as measured by,
5.'LY, s gas thcrmometer. We shall do this luter on (Section 12.2). At this time it
is enough to say that. when Tis e1'prcsscd in ~ unit caned deYI'eu kelvin, dcsignatc<i
by o J{ (which witS introduced before statistic:I\ mechanics wns developed ), the
vahle of the Bolll:lllnnll constant is
Of course, we could mnke I.: = I find measure the temperature directly in energy
units, such as joules or eleclron volts. This is perfectly possible. However, the
tradition of expressing temperature in degrccs, introduced long before the relation
betwcen temperat\lre nnd the molecular structure of a system was recognized, iiS
so well entrenched in physics tha~ it is almost impossible (and perhapil nlsa unde-
sirnhle) to do away with the use of degrees. The quantity (3 is l>ositive (except ill
SOllie special cases), ns will be shoWI\ later; hence the absolute temperature T is
positive. The lowest tempernture is zero, which corresl>onds to what is cn!led
absolute zero.
It must be clearly kept in mind thnt the statistical definition of temperature, as
given by Eq. (10.21), is valid only for a system of particles in statisliCll1 equiliJr.
rium, and hence does not apply to a single particle or to a system which is not in
(I0.25)
~o te that. Eq. (lO:2ii) establishes a relation between the avcrage cnergy per par.
tlcle of a system III statistical eqUilibrium and the temperature of the system.
The exact rebtion obviously depends on the microscopic structure of the system,
which is e)(pres..<:cd in the I)arlit ion function Z, and is different fo r an idcal gas, a
real gas, a liquid, or a solid. I-Icnee we may say that the tempera/ul'e oj a 8y81ellt
in 8/alislical equilibriwn i8 a quantily re/a/e<l to the a~'tra!Je ellergy per particle oj the
.yalem, tJle relalio', def/t-lUlillY 011 Ihe Blrudure oj the 8yalem.
In the general cnse, the avemge value of any p:lrticle propcrty, F(E), which
was defined in Eq. (I0. 12), now becomes
F.'ff. = k, L g,P(E'i)e-K;!!r,
;
(10.26)
and is tllllS a f\lIlction of the tempcrature. For ex:ullple, for the system composed
of I)articles of energies +f
and - f, considcred at the end of Section 10.3, the aver.
age energy of a I)arlicle at the tempemture 7' is
E'.,,,,, = L.. f tanh (f/k1').
Since the exponentinl e- A', iT in Eq. (10.23) is a decreasing function of Ei/k T,
the larger the ratio E,lkT, the smaHer the value of the occup:\tion number 7!i.
T herefore, at a given temperature, the larger the eucrgy Hi, the smaHer the value


446 Cla.,ieal ,Ialil/irel mhaniu (1 0.4 Ttm~ralurt 447

10.4)

of II,. In other words,"the OCeUI)atioll of slnles available to the p..'lrticles decreases IIOTptioll spectrum of molecule!! is observed at normal tel"peratuTC, as illustrated in
as thclr cncrgy increllSCS. At very lOll" temperatures olily the lowest encrgy Icvels J'ig. 5-35 for IIC!. At IlE - 5 X IO -2 e V, thc pOJlulation of thc upper level is alread y
nrc occupied, as shown in Fig. 10-3; but at highcr telll llCratures (corresponding to appreciablc at room temperature, which means that many moll'cull's are in fill cxcited
smaller vRlues of EdkT for a givell energy) the relative population of the higher vibra lional stale at room temperatures. Iiowe"er, for /1"; _ 3 eV, the ratio "j/n i is so
energy levels increases (ngain as "Shown ill Fig. 10-3) by transfer of particles from small that it is plausible to consider the uJ)lX'r level !l.~ essentially l'mpty at u.lItempers..-
lower to higher encrgy levels. At the absolute zero of temperatu re, only the ground tures con.~idewd. Thus most atoms nnd molceules (at room temperature) nre in their
or lowest energy level is occupied. Note thnt the relation of the occupation num- ground elcctronic state. Qllly at ex tremely high temll('ratures, II..!I in very hot stars, nrc
there aLOms and molecules in excit.cd electronic ~l atC!l in any appreciable arnount. In
bers betw~n t.wo energy levels H, and H J is
I Ve'"" \0 .... tcmllernture the laboratory, electronic e.~citation.s are produced by m('ans of illl'lsstic colJisiolls of
1/ .,
tIl = 1J. e-IIi,-Ei) / kT = IlL e-nfo.'/~T,
g;
, gss molecules with fl1.!lt electrons in an electric discharge.
11, g;
(10.27) ..
II,
,
\
f; XAMI'I.E 10.5. Cons.ider a sys tem 01 poilu molecules ..hich Me Ilhl.ced in a uniform
elect ric field, but which arc otherwise isolll.led from any other externalaetion. Compute
where 68 is the energy difference be-
tW~1l the two levels. Thus 11; nnd IIj are
\ the polarizfltion of thc eystem a~ n function of the lemp'.!rature.

comparable on ly if t:.E is much smaller

\h:m kT.
\,.
\~
Solutio,, : Let WI designate the clcetric dipolc moment of each molecule by pO. We
6hall assumc that the effcet of the applied elcetric field i:~ olily to modify the random
orientll tiOIl of the molecule~ without disturbing their trlln~ llltional or internal (rotational
or vibrational) motions, and that the moleeules arc froo to follow the orienting action of
\.y Lo.... ''''''lIf:nlture
the elec:tric field. The energy of a molecule whose dil)Qle momen t makes an allgle 0 wit h
the elcetric field S is 1-:(8) _ -PQ cos 8. Since thc angle 0 csn ha'e allY value betwccn
o and T, the ent~rgies of lhe available statc~ are not discrete but vary continuously. Thus,
,\
\:-,.
instcad of looking for the number of molcculCll oriented nt an anglCl 0, wc must find the
number of molceules with their dipoles oriented within t he solid angle dfi, defined as
Fig. 10-3. i\ laxwell-Boltz.m:mn di.stribu- \. High tempenl.lure bcillg be twec:n cones of angles 0 and 8 + d8 (Fig. 10-4). The value of this solid angle is
tion at three diITeTCnt teillpemtulcs. '......... /" lin - 2"11" .'lin 0 d8, and Llsing Eq. (10. 22) with fJi rcplaced by dfl and the sum mation re-
placed by an intcgral, we may writ(l the I}artition fUllction II!!
o E

Given tempcralUrt~ of lOOoJ\ , 300 K (room temperaturc), and

0
EXAM PL f.: 10.'1.
lOOOoK, de terminc for eauh tempera.ture the ratio betwcen thc occupation Ilumbers for
two le\"els corl"CSlJOnding to t:.E equal to: (a) 10- 4 e\', which is (I, value cquivalcl1~ to the The orientation of the moleeule:! must be sy mmetric relative to the direction 01 the elec-
~padng of rotationnl Jc"els for mallY molecule:!, (b) 5 X 10- 2 eV, "'hich corresponds to
tric field and the average value of thcir elec:tric dilJOlc momcnt is parallel to S. Thus, to
molecular \"ibTl!.tiollallevc1s, and (c) 3.00 c\', which is 01 the order of magnilUdc of I'lce-
find P...., we must evaluate (PI) cos 0) .... , siucc Po cos 8 i~ Ihe eomlJOnent of the electric
Ironic cxcitation of atoms and molecules. ASilume fJ - I. dipole moment ill thc direction of S. Using
Solulio,,' Uellll'mbcringthatk _ .6 178 X 1O-6e\' K-I,wcha\1' thatkT - 8.6 17SX Eq. (10. 26), with the 8ummation replaced
1O-5TcV, and /lE / iT _ 1.1603 X 10 4 t:.f:/ T, \\'hl'rc 61': is expressed in elcctron 'oILs. by an integral, we ha'e
ThercforCl, for thc indicated valul'~ of 6E, thc values of Ilj/ ft, at the three temll('ratures
arClll..!! givcn in the follow ing table.

/lE, eV IOOoK 3OO"K IOOOOK ,

10- 4 O.!)885 O.9!)62 O.!)(l88 pO (roth pot _
kT
loT) .
pof,
5 X 10- 2 3 X 10- 3 1..15 X 10- 1 5.60 X 10- 1
3 X 10- 164 8 X 10-411 8 X 10- 16
3.00 e
a result ,,hleh is called iAnfJtuin'./ormll.ln. At ,cry large or very small lcmll('rature
(that is, for pof, kT), we ha\'e that coth (poS/ iT) ..... I and kT/ po -> 0, so that
Therefore, for t:.E _ 10- 4 ClV, the two levelil arc practically equally lJOpulat.cd at all P... ~ PO. This means that {or a very large electric field, or at temperaturcs nC!l.T !l.bso-
temperatu1"C8 eonsidert'd. This explains, lor example, why the complete rolationala.b- lUll' lero, practically all molccules nre oriented ])&rallclto thc electric field. For small e
 q!,S Cla.uirol '/Cllilficall1l(Coonitf (fO.S
or large 7' (thal is, pof./kT 1), \I'll lise the asymptotic cxpll.u<ion
coth ;!: _ 1/x+x/3+
and thus
P... - Pf,r,/3kT.
If there arc,. 1I10lceulc!! per unit \'o]unw, the polarization of the !ub.~tance i~
G' - np .... - (np5/3kT)f..
T his expression is u&:d in the calculation of the electric I>crmittil-ity of a medium com
]lOSed of polar mol('cull'~. The magnctizntion of a substanL"e ]l1!lCed in an external m!l.g-
nelic field when the lIIoi('i:ules have a ])('rmancnt magnetic momcn~ is obtained by a
similar cl!.lculalion. This i>llhc oricntUion cfT<'Ct which gh'C1I ri:!e to parlunagnctism. In
this case, however, a complication arises. The magnetic moment is related to the allgn]"r
momentum, ,,hich is restricted in orientation, as indicated in Section 3A. Thus instC'ad
of performing nil integr!lolion, we I1lUS~ perform a summation . Thc final result is still
vcry similar to that obtained for !loll l'ieclric dipol!.! moment (Sl'<l Problem 10.8).
10.5 Tllf'r"",1 ~'q";li"r;"'"
Consider a system coml>OSC<l of two different. groups of part ides. We shall SIly that
each group of pnrticles constitutes a $uwy8Iem. Our twO subsystems may, for
example, consist of l\ liquid with a solid immcrsed in it, a mixture of two g:l.SCS or
liquids, or t\\o solids ill contact. 13)' means of collisions find other interactions,
energy may be exchanged between the particles composing the tll"O subsystems,
buL the total energy of the whole system is assumed to be fixed . Let us designate
the total numlkrs of particles in each subsystem by Nand N' and the corresl>orl(l.
ing cnergy levels fl.l'aibblc to the particles by Hit E 2 , 3, ... and " E~, E;, ...
If there are 110 l"ellctioll.lS betwI!Cn the p..'lrticles in the two subsystems, the to!:ll
number of p..'lrlicles in each subsystem is con5tant; also the total energy of the sys-
tem is constant. But the energy of each subsystem is not. conserved beeilusc, due
to their interactions, energy may be exchanged betwccn thelll. T herefore the fol-
lowing contiitions fo r l he two subsystems must be fulfilled by the occupation num-
bers 1110 112, Us, ... , 1wd 'r'l, II;, '13, ... in:l given partition:
(10.28)
N = L lli=consi,
~v: = L nj = consl, (10.29)
i defined I)reci.scly by means of the statistical re\:\tion ( 10.2 1).
U = L ,,;Hi +L n;Wj = eonst. (10.30)
. t. i f;X ,IM /' tt.; W. 6.
T he probability of a given partition or dbtribution is givelL by the product. of two
expressions similar to Eq. ( 10.8), one for each subsystem:
(10.31)
,,
10.5)
We CIUl obtain the equilibrium of the composite system by requiring that. P be a
Thtrmol tquilibriwn
'"
maximum, compatible with Eqs. (10.28), (l0.2{l), and (10.30). The result (see
Example 10.6) is \haL
n',. = _N' ,',-" Hj
Z' J (10.32)
,
where Z and Z' are the respective plutition functions of the t.wo subeystems. \Ve
also note that the two subsystems in eQuilibrium must. have the same parameter (J.
In view of our definition of temperature, Eq. ( 10.21), we conclude that
111:0 ilijJere'lt ami interactiflg syslems oj parlicles in slatistieal equilib-
riwn mrls/lrat>e lJle same temlH!ra/Ure,
a statement called lhe zeroth Imc oj tJlerm(}(ly"amics. It is then Stl.id that the sub.
systems are il\ Ihermal equilibrium. Hence, when we replace (J by IlkT, instead of
E(I. (10.32) we may write
N -8IAr N'
n'. = _ "..,_HI/iT
.
IIi = zflie ' , I Z' J" ,
where l' is the common absolute tempernture of the two subsystems. T he expres-
sions for IIi and IIi sholl' that at thermal equilibrium ench subsystem attains the
samc most. prob.'lble.pnrtition as if it were isolated and at. the same temperature T.
These relations therefore express the fact. that, in a statistical sense, after thermal
equilibrium is attained the cnergy of each subsystem remains constant. T his
means that, although both systems may exchange energy at the microsco pic
level, the exchange takes plilce in both directions and, 011 the average, no net
energy is exchanged in cither direction. T hereforc, statistically, the energy of each
subsystem remains cOnsl:lnl. It then follows that. when two bodies at different
telll lX'T:l.lurcs are I)lnced in contact they wi11 exchange energy until bolh reach
thermal equilibrium aL the same tempernture. At this point no further net. exchange
of energy takes place.
T he ~croth law is the basis of the measurement of the temperature of a body;
ihis temlX'rature is determined by 1)lacing it in contact. with a properly calibrated
stnndtlrd body (or thermometer). The zeroth law is also in agreement with our
COmmon understanding of the concept. of temlX'rature by which, if n. Uco!d" and
a "hot ~ body are placed in cou tact, the cold wnrms up and the hot cools off until
both are ~felt." at the same temperature. Therefore, although the concept of
temperature was first introduced to correspond to a sensorial eXIX'rience which is,
of course, associatcd \\-ith l\ physical condilion of the human body, it cun now be
Derivation of relations (10.32).
So/u riQl" When P is given by Eq. (10.31), if we follow the same procedure used to obtain
Eq. (10.10), we hll.\e
-d(ln P) - L tn n;/g, dn; + L In n~/tIJ dn~ - o. (10.33)
 p

(10.6
'''' Cla.r.ical r/a/uficai nuchanitt 10.6) Application to Ih~ ideal gru

The restric t ing conditions ( 10.28), (lO.29),...a.ud (10.30) noll' gille the 8um by an integral in the form
(1 0.3,1)
( 10.38)

L: dll~ - 0, (10.35)
where geE) (IE replaces flj and rel>resel.!.s the number of molecular states in the
energy mnge betwecn b' and E + dE. This number arises from the different
L E,dn.+ L tidll~ - ;
O. (10.36) oricmtalions of the momentulll p for 90 given energy. :-rom Eq. (2.30) of ElInm-
pIc 2.6, \\"e have that
i\ l ultiplying I::q. ( 10.3-1) by a, Eq. (10.35) by a', and Eq. (1 0.36) by /J, Rnd introducing
these in Eq. (1 0.33), we get geE) dE = 41rV (;~;13) 1/2 r;112 d/~', 0 0.39)

:E, (I n ni!gi+ a+ /1E;) dll;+ L, (In niM+ a' + (JE1) dni' - 0,

where V is the volume occupied by the gas. Therefore
which requires (for the same rc3S011 "in the case of only one kind of particle) tha~

In njlg; + a' + /Jfo:j - O.

Accordingly w{' get The integral nl>l)Cnring on the right can be found (sec Appendix IV) to have the
vulue h / 1r(k T )3. Therefore
, V{2 1rmkT)312
or, USi llg rdBlion ~ (10.28) and (1 0.29) 10 eliminate e-" and e-' Z = 1t3 ' ( lOAD)

No te that we use a and a' \)cc ause the Ilmn\x>r of particles of each subsyswm i~ COlli!C rllCd
separately, but we usc only one fJ becau!!\' it i~ the tota l energy which is conscrn-:d.
10.6 Applicfltifln 10 tilt- ,./I'ttl 1;,,11
Our ne:d, step is to dClenninc whether there is any system of particles in nature
whose collectivc behavior resem bles thc predictions of thc i\ 1a.,(\\cll-Boltlllllfinn
distribution law. Up to this point we havc presented this dist ribution only as a
more or less renSOll:lblc thcorctical construction. Expericnce confi rms the fact
that. most gflSCS cnn be described nccording to i\l:J.xII"ell-Boltllmnnn stntistics OVCI'
a wide range of tC1111>cmturc. For siulplicit.y we shall now consider ideal gllSC!l
composed of monatomic molecules. In this way we do not ha.ve to include the
potential energy duc to lhe intennoleculnr forces nor the cnergy associated wit h
intcrnnl rotational or vibmtional motions of the molecules, nnd nil molecular
energy is trnnslational kinetic; th:l!. is, E j in Eq. ( 10.11 ) is
, 1 ""'2"'"" 2
I~j = -2 Pi = tmVi.
'"
But we nole, as explained in Example 2.6, that the kinetic ellergy of an ideal gil.!!
occupying 1I rather Inrge volume may be considcred as not. being quallti2ed but o.s
having a continuous spect rum. Thererore we \\lust rewrite E{I. (10.22), replacing
which gives the partition function of an ideal monatomic gns as a function of the
temperature and the volume of the gas. Thcll , by taking the natural logarithm of
eneh side, we have
InZ=C+ilnkT,
where C includes all\he remaining constant quantities. Substituting this value of
In Z in Eq. ( 10.25), we obtain the average energy of the molecules B8
(10.41 )
Therefore the average kinetic energy of the moleculcs of an ideal g1l8 in stll.tistical
equilibriUlIl is proportional to the absolute temperature of the g!\.S. iI istorically ,
Eq. ( 10..11 ) \l'lIS introduced in the nineteenth century, long before the development
of statistical mechaniC!!, in connection with the kinetic theory of gases. It was
this relation that suggested the identification of fJ with I/k T. The total energy
of a gas COlliposed. of N molecules is then
( 10.37) We conclude lIlCn that the internal energy of nn ideal monatomic gns depends
only on its temperature. This is u direct result of our dcfinitions of an ideal gas
and of temperature. We do not expect the .':UllI(' rt'latiolls to hold fo r real gases or
other subst:UlCCS, since thC'ir internnl energy is p:"lrlly potelltial and thus dcpends
Oil the separation of the molecules; th:lt i~, 011 the volume of lhe substancc.

'\
 ...
[10.6
10.6) ApplicatiQlI /0 the idt(J1 gus '53
Clauicalllol~lirol
'"
mWlollin
,.
'"
Fig. 11)-6. ;\Iolcculnr velocity di~tribu
IlXJ' K _ Fig. 10-5. l\lolecular energy distribu- tion for oxygen III t\\"o lcmpcrrillll"Cl! (80 0 K
tion at tw o teml}Craturc~ (I00oK and lind 8oo0 K). Note, fronl Eq. (1 0.45),
3001\:). Note, (rom Eq. (lOA 4), that the t hllt the veloeit.y distribution depends on
cucrgy distributiou is inclepc.'nd(mt of the the molC(:ular nI/lliI!.
molecular mass.

:lOO"'"
T _ SOO"K

, [-"L;,,,--,,;\.,,;---i3.~":::='~.';)=;;5.~"=';'"i.C;):;7~"::~,<?i;, o
(10:' ,II ~-I) " "
f (111- 1 I'V )

I
Sometimes we require the velocity distribution rather than the energy distribu-
Ir N is the number of moles" of the gM, and N ,\ = 6.022;; X 1023 moic- is tion. Noting that }.J' = ~II!V2, we then have that
Avogadro's cOllst:lIll, which is the number of molecules in OIlCl mole of the sub-
stnnec nnd which is the &'UllC for all substances, we have N = N I N,I.. Thus dn
m-ll
(10.42) dB
U = !skN",\T = ,sRT,
where ;\ Iaking the substitution B = tllw2 in E<I. ( 10.44), we get
R = /':N A = 8.3143 J moic- 1 01\_1
= l.!)$(i() calories moic- I 01\:-1
d~=4 ,V ~ '" 2_.., 1 2~T
= S.IS!).! X lOlg cV 111010- 1 01\-1 (10.-13) du 7t. ( )
27rkT u e , (10.45)

is called the gas conslant. which is IHaxweU's formula for the velocity distribution of the moleculcs in nn
Expression (10.23) for the distribution of molecules among the different ellergies,
ideal gllS. It givcs the number of molecule~ moving with n velocity betwecn v and
with (Ji I'cplaeed by 0(8) dE tlI; givell by E;q. (1O.3!), is nOli"
v + dv, irrespective of the direction of motion. Thc velocity distribution for
_ N
dn - Z e fI
~I 4 7f1'('_m
_ _ EIl:T (E') dl' _ ~
~ - Z h3
'J'" ,,,1/2
~ e
- " I ~TdF
~,
oxygen at two difTerent temperature.'! is represented in Fig. 10- 0.
A crucial lest of the applicability of ~Iaxwell-Boltzillann statistics to ideal
gnscs i.'! to sec whether the energy and velocity distributions illustrilled in Figs. 10-5
where du is the number of molecules with energy betwccn E and H + dE By lind 10-6 actually occur. OtIC indirect way of doing this is to analyze the depen-
introducing the \alue of Z as givcn by Eq. (10..10), we h:we dence of the rate of chemical re:lctions on the temperature. Suppose that a par-
ticular reaction occurs only if the colliding molccules have a certain ('nergy equal
tin 27tN 1 ,1 12 _ f: /tT (10..... ) to or larger than }:~. The rillC of reaction at n ghen 1eml>crature then depenilil on
dE = (7rk7')3/ 2 ~ C ,
the numbe r of molecules h:wing lUI energy equal to or larger thlln E. These num-
which is ;:-'lax\\c\l's formulrL for tl1(' ('n('rgy di:;tribution of the molecules in lUI ide:11 bers, for two difTerent teml)Crltture~, lire givcn by the shaded areas under the low-
gas. T his constitutes one of the ('arlieosi applications of statistical methods in teml>cmture and high-tempemture curves of Fig. 10- 7. We note that. there are
physics. Jt was originally derived by J:l1l1e~ c. ~Iax\\"ell around IS:>7, using a more molecules !lvaihble at high than aL low temperatures. By proper calcuh-
difTercnt logic. A ploL of Eq. (10..1-1) for t\\"o dilTerent temperntures is represcnted lion, we can predict the effect of these addition:11 molecules, and the theoretical
in Jiig. 10-5. prediction can be compared with the eXI>criment:Ji dal!l. I~xpcri!llcnt:ll results arc
in excellent agreemcnt wilh P.I.]. ( 10..1.,); this confirms the applicability of ~ I:!.x\\"ell-
Hecall that 0111' mole of a 8 ub~UlllCIl ii fin amount of thllt tiuo"IIUUX' , in &ram~, equIII to Boltzmann statistic;; to g:lSC".
ils molecular ma.'!S CXPrI';:;',;('(\ in &mu.

.
 Claniwl rlali.sliwl mhaniCl (10.6 10.6) App/iw/iofl /0 /hi! idmi fIIU 455

d. equilibriulli at the tempemturo of the reacto r. Neutrons in :l thermal nuclear

dE
, tCnctor thcn behave a;j an ideal gas a nd thei r energy distribution agrees with
~l llx\\"e l l's 1aw, Eq. ( 10.44 ); that. is, the rmalneutrollS fol1ow " l axwel1-Boltzmallll
statist ics. This fact is essential in nuclear reactor d esign. If the neutrons emergi ng
from u porthole in u reactor lire Illude \.0 pass through II. chOI)pCr similar to tha~ of
Fig. 10-8, a mOI)ocncrge t ic beam of neutrons is obtaincd.

Obtain the most Ilrobable encrgy and velocity of the gas molecules
f.' X ,,' M I'I.f; 10.7.
a~ a given temperatufC; these values rorresjlond to the mllXimll. of dn/ df..' and dn/ du
n.'SllCcthely. '
So f.. ri<m : To obtain the maximum of dn/ dB, given by Eq. ( 10.44), at a certain tcmllCta-
o ture, it is nccessary to romllUtc only thc maximum of II _ B I / 2f! -lIn r. ThUll
112
Fif!. 10-7. Number of molecules with energy larger than E. at two different tempera- dy _ (J../<.'-1I2 _ 8 ) _.,.r 0
de 2"' feT f! -,
tures. The number in ellch case is indieatcd by the shaded area.
from which lI'e have E",p _ itT. T hu~ 11.1. room tempcrature, for which kT...., 0.02.5 eV,
A morc direct verification would consist in an actual "count" of the number of we hllve Emp"'" 0.012 eV.
molecules ill each energy or veiocit,y interval. Several experimental arrangements Similarly, to obtain the mllXimum of dn/dv, gi vcll by Eq. (1 004.5), \I'C must compute
the maximum of OJ _ v2e-..,2~r. Th(!n
have been used for this purr~")se. One method , using a velocity selector or "chopper, n
is illustrated in Fig. 10-8. T he two slottoo disks, D and D', rotate with an angular
velocit y wand their slots arc displaced by an angle O. When gas molecules escape
dy
d =
(2u- W3) e_,".'/2~r -0.
lIIu

from an oven at a certain temperature (a process called ejJlUion), they pass through
both slots and are received at the detector only if their velocity is II = 3<JJ/ O. Actu- Therefore ~_p - ~. This velocity corresponds to lUI ellergy E _ kT and is there-
ally, since the slots have a finite width, the transmitted molecules have velocities fore different from i:: .. p ' Can the ~t udent ClClIlain the reason for this difference?
in a certain range .611 about the given value. When either w or 0 is changed, the
velocity of the molecules received at the detectors can be changed. If one makes eXAMI' U '; 10.8. A,'eragc velocity (r....) lind root.-mean-.'Iquare velocity (I~ ...) of the
severnl observations for different velocities v, the velocity and energy distri bu- molecules in all idcal g&.'!.
tions nrc obtained. The experiment:LI result.'! confirm the prediction of i\ laxwe1l- Solutio'l: The average velocity is defined by
lloltznlnnll st:ltistics, as expressed by Eqs. ( 10.44 ) and ( 10.4 .').
A.5 explained in Section 8.G, neut-rons I)roducoo in the fission process in fl. nuclear
tCnclor :l re slowoo dowll by mcnn.~ of a suit:lble modcrntor until they nre in thermal
v... = -
No
!
j," I
vdn __
No
j," v -dn d.
d

Introducing the vslue of dn/ dtJ gh'en by I::q. (10.4.5), we ha,'e

Effusing

C~~r h:_::'~"'''' r _ ., (~)'" [ 0 3 __ .' /2.r .J_

r:J\ .1 J ----i~--- L----~ We first trsn~form

........ Z.kT De IW.

the iutegrlll by selling u _ u2, so that du _ 2D dl', rc~lIlt i ng ill

~ II 11=';:: 1 Detl"<:Wr i 10" 14e-{,"/UT)" d14.

'--.. ~
L"olii",,,tllllo: \...... /) f}' Ne~t we integrate by pllrUs, r('~ulting in ;(2k1'/ m)2, ~ thllt
.lIhl

Fig. lo-tI.
nouuing disk.<

~ I olecu l(l.r yelocity selector. ,..... -(SkT)'"

-./11 - (2.55'T)'"
--
1/1
- - 1.1&", P.

t
 po

". Claujcal ,/oli.diwl muhanicr

Problmu
'"
do 7. FUlldamtlltal. of Sia/i.lical Thn-modyrw.mic., R. Sonntag and G. Van \\'ylcn. New
d. York: John "'iley, 1966, Chapters] and 2
Fig. 10-9. Most probable, average, 8. S/II/illicai Thn-modynamic., E, SchrOdinger. Cambridge: Cam bridge University Press,
\
....
and roolrmean-square velocities of a 1964, Chapters I and 2
9, Tht Ft/Jllmall L/lirt. all Ph/J'ic" Volume I, R. Feynman, It Leighton, and :\1. Sand;;,
Heading, ),Iass.: Addison.Wesley, 1963, Chapter 40

I'robl""r ~

We define t.he root-mean-squarc 10. 1 Referring to E:o;ample 10.2, find the sys tem (1\'ith f/; I) il$
Of..I1~
from the cx]>rc!lSion change in the probability of the distribu.
Z _ ( I _ CIl1)-I.

,
(lI) ... - No
I
1",
lld 'i.
tion il tll"O particles, one from the upper
and one from the 10ll"er levcl, flre trans-
ferred to Ihe intermediate Icvel. Repell.t
(b) Compute the average energy of the par+
ticle~. (e) Find the limiting value of the
for the most probabl(' partition found in average energy "'hen ~ is much smaller
Exalll]lle 10.3. than kT.
Noting that 1/ 2 .. 2E/m, we may also write
10.2 III Exam])le 10.2, compute the ralio 10.7 Consid(,l"ing a system of particles

(v) , "1"
...
___
"IN (I
Bdll--"&",,,
'E
>II
P2 / PI, u~ing Eq. (10.13) for In P.
10.3 Determine the temperature of Ihe
system of Example 10.3 when it i~ in sta-
having en(!rgies O,~ , 2~, .. , ,n~, ... ,plot a
graph showinf!; the occupation numbers [or
(a) 1001(, (b) 3001(, (e) 800 o K, given
tllM the value of lhe cn('rgy t is (a) 10- 3 eV,
liince the average energy i~ detine( I byo..... - ( l iN)!'; dll. But for an ideal gllll, accord- tistical equilibrium. Assume t - 0.02 eV.
(b) 0.1 eV. [Uinl: UiI(l the result of Prob-
illg to 1-:<1- (1 0.44), E .... .. jk7'. Thus lOA Find lhe ralio of the number of elec- lem 10.6 for the 1l!l.Ttition fUllction.]
trons having their wins parallel l!.lId anti- 10.8 The magnetic moment of atoll'" (or
parallel to a magnetic field AS a function o[ molecule~) having 1111 angular momentum
Ihe temp'erature. E,'alnl!.te the number for ) i! givell by Eq. (3040): M - - psg) .
and a temperature T equal to 10, 300", and (a) Obtain an expression giving the num-
~,_ .. (~nI 12 1000"1\. IHint: Recall that the "pin mag
netic moment of the electron'! is gh'en by
ber of atoms having a \'aluc of J, equal to
"''', if the atom$ are placed in a magnetic
Ms - - 2p B S, Eq, (3.33).J field moriented parallel to the Z-axis. (h)
The three velocities, II v."'" and \',_ are itldicated in Fig. (10-9). 10.5 (11.) Show lhat the partition funetiOIl Sholl' that the l)3rtition [unction of the
of an ek~tron gas Illaced in II. magul'tic s}"lItcm of alom~ is
field ffi is Z - 2 cosh u.uffi/ kT), whl're,lll!
i3 II. Bohr magneton. (b) Compute the z _ si uh Hj + ! ),111l9<B/ kTI
IIeff! rf'n C f ! 1f magnetic energy or 11.11 electron gas in the sinh [!,IIuQ(B/ kT]
magnetic field; then show that Ihe pam-
"What. is I'robabilily?n R. ClUllal>, &i. Am., Septemocr 1953, page]28 (c) Verify that for j - t thc partition
magneti~m of fl"<'t' electrons corresponds to
~: ~ThcrmodYllamics, Stali~tice, and information,n L. Brillouin, Am. J. Phy&. 29, 318 a magnetization JI _ IIPu ianh C,IIu<./ kT),
function reduccs to that obtaiued for elec-
trons in Probl('m 10.5.
(1I)G1) . where n i.~ the Ilumber of ekctrons per unit
. .111 Statl$tlca
. . . I i\I volume, (c) Hnd the limiting \"al\L(,~ of 10.9 OIJtain the average magnetic energy
3. ;'1'hc Work of T. 11. Bcrhn I cc1lallles,
. "111
..Kac
, PhySIC' Today , Octo-
~I __ . the partition function and the mag_ of the atom$ eon~idered in the preceding
Iletization at vcry low and \'try high problem. Verify from this result that the
4. "New Al>proneh to Statistical )'Icchanics," lL Weinstock, Am. J. PIi!J" 3.., 710 Iwersg(' magnetic moment of the atoms in
tempcl"ature~,
( !fl07) a directiou parallel to the msgnetie field is
10.6 The poS:!ilJle ]larticl(' encrgi(,J! of a
5. SIQI~tical.llc(:hllllic., G. Rushbrooke. London: Oxford Unive rtiity I'rl'S3, 1949
system of psrlicles arc 0, t, 2t, ' .. , lIt, ... .If....
6. Sta/i.lical Ph,ne.,G. Wannier. New York: John Wiley, 1966, Chn.ptcrs I, 2, lionel 3 (11.) Show that the partition function of the - ~1\g[U ; ) coth U + ;)% -! eOlh !..t[

...
 ...
Probltm, 459
458 Cluuirol "alu/ital nw:hullicr
\ 10. 18 Show that the number of molecules
TAHLt: I(H Va lues or err (.f). 10.28 Uijing the result of Prohle l\l 10. 25,
where x '" lJ.u<;&jkT. Fiud the li miting find the l)('rcentagc of molecul!l!! of an ideal
vnlues of .1f for x \'I'ry small and \'ery of an ide lll gas moving \\'i th vdocity having
eomp.onents in the range ~, and v. dl'., + , erf (x) , erf (x) gas th nt. ha ve an energy larger than 0.5 cV,
large compared with I .
/ 10.10 At what temperalllre is the lIumlx-r
v. and v. + +
dV. J I'. and I', dv., is given by
0 0 1.6 0.4882
gil'en that the temperature is (a) 3OO 0 K ,
(b) OOO&K , (c) I,OOOK. [/lint: Note that
of moko.cules of an ideal gsg per unit en('rgy )3 . ~ __ "I ~T.1_ d d 0.2 0.1113 1.8 0.4946 in th(' ('.~ pre!<>'ion deril'ed in Problem 10.25,
dn .. !I (m/2"1fkT l '"'. v. v,. 0.4 0.2 142 2.0
range at 2 X 10-: eV, one-fourth of the 0.'1977 z .. ( EkT) 1/2 .J
number corl'('!!ponding to I X 10-: 1','7 0.6 0.3019 2.2 04991
[Note that, in E(I. (10,45), for this case we 0.8 0.37 !I 10,21) Show that the number of gas moJo
2.4 0.4996
10.11 Find the ratio of the number of must replace the int('gra tion e[('ment
1.0 004214 2.0 O.'!!)!)!) ecull.'ll with velocity betWC('1l 11 and v+ dv
molecules of all i(leal gas I)('r unit energy 4"1fv2 dv by dv, dl'. dl'.> Justify this re colliding with the lI'all of n co ntllinl'r, per
1.2 O .~552 2.8 0.5000
fang(' at. encrgic~ of 0.2eV and 0.02eV, 1)lacemcnt.] unit. area and per unit time, is tv{dll j dv) du,
,.4 0.'1762 3.0 0.5000
given that the gas temperature is (a) 100)(, T hcn show lhat the totnl number of mol
IO.I!) Sho"' that. the number of mole-
(b) 3OO0 K, (c) 6OO0 K. cules of an idcal gas that ha"e an X ecull'll colliding "-ith the \\'alll)('. unit t ime
For larger \'alues of x, the values of
10.12 Coml)lIle ('nollgh points to con component of vdocity between v. and ('rf (:1') r{'maill constant at 0.5000, Ull to i.i !-IIC...., wllcre n in both ea..~cs r(''TS to the
@t rllct gral)hll of thc mole<:ular energy dis v. + dc, irN'!'peetive of the valuCli of the four ~igllifieant figures. numbl'r of molecules Ill"r ullit. I'olume,
tr ibution function in an ideal gsg for onc ~. and v. components is Note that the lllolecul(,l1 with " elocity II
kilomole at 200 1{ and 6001{ . colliding Il<'r un it area lind I)('r unit time
do _ N(III / 2rk T ) 1/2 ~ .....!n 10.23 Compute the fract ion of molceule~
kT d an d moving in a direction making an angle
10.13 (a) Compute thl) rooL-1IIeiUlsq uare, v,.
of an idclLl ga..~ that. hlLVC Il vclocity with a 8 with the normal to the "'all li re those
average, and most. probable \'elocitie~ of
[I/inl: Integrnte the expression obtnined in componcnt along the X !ui~ (a) smaller within a cylindrical volume of height
o:.:ygen 1II0lo:cuies at a tempcrat ure of
Problem 10.18 owr r. and ",. T he limitJI tha lL t ,.p, (b) larger than 1'.1" (e) ~maller equal to ~ co.s 8. Also the fract ion of mol
3OO 0 K. (b) Compute thc most Jlrobable
veloc ity of oxygen molet"ul~ at the follow. of integration in each <:a.c must. be from than v...., (d) larg('r than f.....
[/lint: See eculc" moving with in the z;olid aliKIc df! is
- ~ to +~1
Problem 10.21.]
ing temperaturt.'s: 10000K, 300"K, 1~)( ,
10,0000K. 10.20 Use the result of Problem IO.I!) to 10.24 \\'hll t fraction of the molecules of df! .. 2"1f sin 8 d8.
lind
10.14 (a) Compute the I11can translational obtain the 1!.I('rage I'alue of (n) I'.. (b) I'~' an ideal ga~ have X.-comllOllenta of vcloc
kine ti c energy of an idcal ga..~ molec nle at. (c) Iv.1 for an ideal gll~, it.y \x>t"'('('11 - v'"" lind +",",,1
3OO 0 K. (b) Compnte the root--1IIcan--!!quare 10.21 The crr(Jr jUnctioli (rf (.1:) i ~ dcfmcd 10.25 Sholl' that.the lIumlx'r of molecules
JO.ao A~s\l!ne that a small holc is made in
the wall of a n oven containing It. gas at
velocity if the glls is hydrogen ( lb), oxy
gen (02), or mercury vapor ( Ug). Comp~re
your result.;s for hydrogen and oxygen wnh
by

ed (.1") .. -
1
y.o
"
I
,
_.~

"".
of an idt'al gas that hnvtJ a \'(,Iocity be--
tween zero and v i~ given by
te nll)('ralUre 7'. Show that the number of
mol('cuh:'$ with velocity between II a nd
,,+ du escaping per ullit area and per
the velocity of f!Ound iu those ga."es.
.
10.15 Compute the rooL-mean--square I'e
In Table 10- 1 we give some vnlues of this
N(O,") - 2.V [erf (x) - ;; l'e-" ], unit time is

locity of (a) h('lium ato ms at. 2"K, (b)
nitrogen molecules at. 27C, (c) mereury
atoms at 100C.
10.\G At what tt'mp('rllture is the mean
/ trllnslational kinetic ('ncrg)' of a molecule
of an ideal gsg equal to that of a singly
charged ion of the ~ame mass that. has
been acccl('rated from r(>st. through a po...
tentilll difference of (a) I voit, (b) 1000
1'011.3, (c) 1,000,000 I'oll~? Nl'gl('ct rclllli
vistic cffectJI.
10.17 Determine the fract ional number of
mol..cules of an idenl glloS with velocities
bet\\'cen I.'ao. and 1.2l.... from Eq. ( 10.'15)
making (a) " .. r.... and d" .. 0.2r.. ... ; (b)
" .. 1. h and de .. 0.21......
function. U singthere~ultof Problem 10.19,
show that the Ilumbcr of molecules of all
i\l('al gas having al\ X~omponel\t of veloc.
ity between 0 and ~. is
N(O, r.) .. N erf (x),
where x .. (m / 2kT) I I2V., and the number
of molceules having nn Xcomponent of
l'e1ocity larg{'r thnll I'" is
N(v" ~) .. N[! - erf (:l)).
10.22 What fractioll of the molecul<'S of an
idea! gas have po.itive Xeoml)()ncnls of
velocity grt>ater than 2t. p !
( )'"
m 3 - " " nkTd
where:l~ .. mv2j 2kT. ,Uso find the num . . dn _ "If! 21rkT ve v,
"
ber of molecul('s that have a I"elocity
larger th a n v. [lIilll: U!\C Cq. (1 0.45) ;'lnd wherc N gh'cs lhe total number of mole.
integrllte by 1}IHL~.1 culcs lX'r unit volume in the oven. Find
10.26 Usillg the TC!lult of Problem 10.25, the total num\x>r of molecules escaping
compute the fract ion of molecules of an liCr unit area !lnd lief IInit lime. Also
ideal glPoS that hal'e a \'elodty (a) smaller show thaL the average IIlId rootmClln
tha n Pm", (b) larger than ~ .. P' (e) smaller !!C)UMC Illolecular velocities in the outgoing
tha n ~' , (d) larger t.hanv.,... ocam are
10.27 Wha t pcrcentag(l of oxygen mole. .
3 21fkT
cuies have v(' locit;c;s gr('ater thall 103 m S-I t.... ~ 8
at a temperature of (a) 100oK, (b) I,OOO"K,
and
'"
(e) 10,000"J{? lllu~t rate graphically in
terms of the distribution function,

460 Cialli(ai,lalidiwl muhalliu
Compare with the corresponding vlIlues
for the molecllles inside the O\'en and make
a critical evaluation of the results of the
experimell~ ilIustrnted in Fig. 10-8. (Hint:
Use the results of the precetliug problem.\
10.31 (a) Show that thc del3rogJie wave-
lellgth for a particle of mau 1/1 mO\'ing
with the mO$t probable velocity of II max-
wellilln distribution at te mllC'raLure T is
~ _ h/( 2mkT)1I2, where k i~ Boltlm:um's
constant. (b) Calculate the de Broglie
wavelength of a neutron moving with lhe
most probable sl)(!(!d of a maxwcllilln dis-
tribution at Wo e. Compare these wave-
lengths with the interatomic scpnr(!.lion in
a solid.
10.32 What fraction of (a) 11 atoms, and
(b) HCl Jlloleculc~ would be iii the first
excited stille at 3OO 0 ](?
..
10.33 Suppose that the energy of the mol-
11
ecule! of a system can be eXllrcsscd as a
sum of two terll15; that is, THERMODYNAMICS
E,' - Ei ... + E. I.,
where H,.ureters to the translational motion
lind E . I ., rcrer~ to the internal degrees of
rreedom (such as the rotation and vibra-
tion of a molecule), or to the interaction
with an eleclrie or magnetic field. If gl. ,.
and g ,<I' are the intrinsic probabilities eor-
rC!!pouding to both types of motion, we
have that g. _ g'.,o9l.I .,. Show that: (a)
Z _ Z"Z;"" where Z is the total partition
function snd ZIt and ZI., Ilre the trllnslll-
tional Ilnd interval partition functions;
(b) U - V,. + V,n<'
11.1 JnlroduclioTl
11.2 Conserval.iort oj Energy oj a System of Particles
11.3 Many- Particle Systems; Work
11.4 'Hany. ParlicleSyslems; Heal
11.5 The First Law of Thermodynamics
11 .6 Graphical Representation of Processes
11.7 Special Processes
11.8 Entropy and the Second Law of Thermodynam ics
11 .9 entropy and H eal
11.10 Discussion oj Processes in Terms of Entropy
 pi

(11.2 11.2) CollferMlioo of eTlugy of a ryl/em of particle' 463

T~rmod.Yl1amia
""11.1 Inlrodudion
to the center of mass of the system" as internal kinetic energy; that is,

I n Chapter 10 we developed a statistical model for handling systems of many Ekin. = L: ;m,'I)~= ;ml!l~+!m2!1~+;m3l'~+'" (1 1.2)
identical components; this was called Maxwell-Boltzmann statistics. We illus-
trated this model by applying it to 0. special example of llQnin/traGting particles:
."
1>'''';oI~.

the ideal ga.~. B ut the particles we find ill nat ure arc always interacting among
themselves. T hus the next step is to discuss assemblies of intcmcting particles,
such as Moms or moleeules in the solid, liquid, or vapor state, or even the nucleons
in a nucleus. Equally important, we wallt to establish a correlation between the
predictions of statistical mcchanics and the quantities we measure or observe ex-
perimentally at the macroscopic level. Also, instead of considering an isolated
8)'l!tcm in statistical equilibrium, we wallt to find what happens when a system
interacts with its surroundingg, since this is the situation that is most. common in
nature.
This gap betwccn statistical mechanics and the macroscopic properties of mat-
ter is bridged by the branch of physics called thermodynamic8. Historicnl1y, the
science of thermodynamics dcveloped during the eighteenth nnd nineteenth cen-
turies (before the introduction of statistical methods) WhC!l the notions of heat and
temperature were not yct well understood. It evolved as a rather formal and ele-
gant thco ry whose results and methods became extremely important for engineer-
iug purposes, due to the development of heat engines at about the same til)'le.
Thermodynamics reached its climax at the end of the nineteenth century, with the
work of Carnot, Joule, ](elvin , and others, just at the time when statistical methods
were beginning to be introduced through the work of l\Iayer, Boltzmann, Gibbs,
and others. The development of statistical methods and thei r application to
chcmical processes have madc a revision of the formulation of thcrmodynamics
necessary. However, from the point of view of its applic.'l.tions, no essential changes
have been introduced.
] n this chapter we shall consider thermodynnmics from the point of view of
statistical mechanics.
Not~ lhnt ~q. ~11.2) , corrcs]>onding to the kinelie energy, has one tcrm for each
partlcle ~ whIle E,q. ( 11.1 ), cor~s l)Onding to the l)Otential energy, hlUl one tcrm for
each llalr of partICles, because It refers to two-particle interactions only Then the
lolal internal enery" U of the system is .
U = Ek in. + Ep Lnl' ( 11.3)
For the. case of an ideal gas, there are no intermolecular forces and the internal
energy IS just the kinetic energy. In some instances the potential energy can be
cxp~ssed as a sum of single-pMticle terms, as indicated in Section 10,2. This is
pOSSIble when, to a first appro imation, the interparticle l)Otenti:ll energy cnn be
7
replnced by !m avcrage l)Otelltml energy for each particle. If no extcrnal forces
net on the particles of the system (Le., if the system is isolated from external
nc tions), thcn U docs not ehange. In othcr words:
The illtenlal ellergy oj all iwialed system oj l1artide8 remaiu8 COllstallt.
When there are external forces acting on the particles of the system the internal
~nergy docs.not.. in general, remain constant. Suppose that the syst~m is initially
In n. state WIth Illternal energy U o. The state of the system is continuously modi~
lied by th~ external forces, so that after 1\ ~ rtain time the internal cnergy is U.
Lc~ us dcslgnate t~e total work donc during the sallle time by the external forces
nctmg on the partIcles of the SystClll by W~:... T he work W""~ is a sum of many
terms, one for each particle subject to an external force. T hcn conservation of
energy requires thl\t
U-U o = IV""" (1104)

11.2 Comwrr:ation 01 finery" 01 a Sf/stNn of '-article. which states that:

Let us consider a system of particles subjl.'t:t both to their mutual interactions and The dtangfl i ll lite in/el'll(ll elleryy oj a 8y8/em oj IXlrticie8 i8 equal 10
to external forces. The system ml\)', for example, be a single hydrogen lllolecule the tcOrk done on the 8y81em by the external Joru8.
(in which ease the component pnrticies are two protons and two electrons) or a
gas contai lling a lMge mEmber of hydrogen molecules. ] n the latter case, the par- It may ha~pen that even if there arc external forces acting on the system, their
ticles eomposing the systcm are the molecules; thus their internal structure may tO tal,work IS l,cro: lV u t = . O. In such a casc there is no ehangc in inlemal energy;
be ignored in fl first ap proximntion. Given that Bpi; is the l)Otentinl energy due ~hnt IS, U = U o. If work IS done 011 the system (lVn positive), its intemal energy
to the interaction of pnrticles 'i nnd j, thc inlen/al potential wer{JY of the system is lIIcrease8 (U > U o), but if work is done by the SystCl1l (lV. x negative), its inter-
nnl cnergy decreases (U < U o).
Epi .. ~= I: b'pij= Epl, + EpI3 + + Ep23 + ' ( 11.1)
."
pa,n ~ To eXI)~e~ lhe kin.ctic cncrgy, wc have to define a framc of reference since otherwise
lUI value Ci mdetermlnate. '
Similarly, let us designate the sum of the kinetic energy of the I)articlcs referred
 ...
H.3)
Thtrmod;ynamia (11.3
Many-par/iell 'YI/eml,' IOOI'k '6'
To compute this int.egral, we must. know the relation between p and V. This rela-
11.3 ltlnng-Iarllcle SII"Il!IRiI; Work
tion has been studied ill great detail for gases and other substances, and we shall
The systems we consider in thermodynamics are composed of a very large number consider it later on.
of particles, and therefore calculating the cxternal work as a sum of individual Obviously the extemnl work done on the gas is
works on each particle poses scriOU.5 difficulties. For that reason it has been found
convenient to express IVeU as a sum of t"o terms, both of a statistical nature.
,
Wed = ~ ( pdV. (11.8)
One is still called work and thc othcr is called MaL Very often, especially when I.,
we are dealing with thermal engines, it is preferable to compute the cxt-emal work
done by the system, dellot.ed by Way,,, instead of the external work done on the Let us now recall some of the more common unit.s in which pressure is expressed.
system, IV..,~. Since both works correspond t-o the same displacement but to Note first that pressure must be expressed as a unit of force divided by a unit of
forces equal and opposite, the two works are equal in magnitude but have oppo- area. Thus in the:'ll KSC system, pressure is measured in n<!wlonl per square meter,
site signs; that is, lVoyu = - lVu~. In the future we shall write 1V instead of or N m -2. Other unit.s fT'C<luently used nre dYIICI per square cUllimt!ier (dyn cm -2),
1V .yot fo r the work done by the system. and pound8-force per 8quare inch (Ibf in- 2 ). Another useful unit, used mainly for
expressing the pressure of gases, is the a/mwphere, abbreviated atm, and defined
according to the equivalences

One atmosphere is npproximately the normal pressure exerted by the earth's

F ig. II- I. Work donc during expnnsion ntmosphcre on bodies at sen level.
of a gll.3.
EXA MI'I.: /1.1 . A gas occupie!l a volume of 0.30 m3, exerting a pressure of 2 X 10~
N m- 2 The gas expands to a volume of 0.'15 m3 , while the pressure remains constant.
1-"'-1 Find the work done by the gll.3.
Consider, for exam]}le, a gas inside Il cylinder (Fig. ll~l). The gas can exchange Solufio" .. We use Eq. ( 11.7) and, when the ])ressure p remains constant,
energy and moment.um with the surroundings through the collisiollS and interae--
tions of its molecules with the molecules of the walls. The exchange of momentum , "
W .. I. p dV - PI. dl' - p(l' - Vo). (11.9)
is rel)rescnt.ed by a force exerted by each molecule at. the point of collision with v. v.
the walL These individual forces fluctuate at each point, but because there are a
great lIIany collisions over a large area, the overall effect can be represented by This resul~ is completel}' genersl and applia to any system whO!C volume changes under
an average foree F acting on the whole nres. The pressure p of the g38 is defined a constant J>~ure. I nserting the numerical "slues, we obtain

p = FI A .
M the average force per unit area. Then, given that. A is the area,
, /0'= pA . (I Ui)

If one wnll of the con tainer is movable, such as the piston of Fig. II- I , the
EXAMI' LE /1.2.
Jr - 3XJ04J.

A gas expands in Such a way lha~ the relation pV _ C (constant)

holds. This relation requires that the temperature of the gas remain constan~, and con-
force exerted by the gas may produce a displacement dx of the wall. The exchange stitutes Boyle'. law. Find the work done when the volume expands from V 1 to V 2.
of encrgy of the systcm with the outside world may then be expressed by the
work done by this force du ring the displacement. T herefore & IUl io" .. Using Eq. (11.8), we obtain

dlV = F dx = pA dJ: = p dV, (11.6) ", r'. c dVI' _ In -v,v,

where dV = A dJ: is the change in volume of the gM. Then, if the volume changes
from V 0 to V , the external work done by the gas during the expnllsion will be
lV_
1 v,
pdV_
),"
(lI.lO)

Therefore tI,e work done depends on the ralio 1' 2/ V , between the two volumes (this is
called the expaJlS'ioJl falio). I n the design or internal combustion engines, the compressioa
IV = (vpdV. (11,7) (or expansion) ratio is one of the factors which detcrmine the power or the engine.
I.,
 ...
(11.4
Thumodynruniu
It is important to benr in mind that Eq. (1l.7) expresses a macroscopic average
which sums all the individual exchanges of energy between the molecules of the
gas and the molecules in the piston. But how docs one compute the exchange of
energy which occurs due to the interaction of the gas molecules with the walls that
remain fixed? In this case the method used to evaluate lV for the piston docs not
apply. Although we may still define an average force on the wall, we cannot define
an average disl>iaeement of the wall. At each individual interaction between the
moleculcs of the gas and the wall, a small force is exerted and a small displacement
of the molecules in the wall is produced. If we could compute each olle of these
infinitesimal amounts of work and add all of them, we would have the correspond-
ing external work done by the system. However, this technique is obviously al-
most impossible because of the large number of factors involved. Thus we shall
define a new macroscopic or statistical concept called heat to account for such work.
The avcrage value of the external work or encrgy exchanged between a system
and ita surroundings due to the individual exchanges of energy which occur as a
result of colli!;ions bet.wcen the molecules of the system and the molecules of the
surroundings is called heal, Q, whencver it ennnot be expressed m:lcroscopical1y
as force timcs distancc. Thcrefore Q is composed of a sum of many very smnll
individual external works, such that thcy cannot be expressed collectively as an
average force times an average distance.
According to the sign convention we have adopted, the heat Q is considered
positive when it eorresponds to a net extemal work done QIt the system and nega-
tive when it is equivalent to II. net extemal work done by the system. In the first
case we say that hent is abaorbed by the system and in the second case we say that
heat. is given off by the system.
Since heat corresponds to work, it. may be expressed ill joules. However, heat
is often expressed in a uni t called the calorie, abbreviated cal, whose definition wa.s
adopted in HUS as I calorie "" 4.1840 J. The calorie was first introduced a.s a unit
of heat measurement when the nature of heat was not clearly understood. But the
ealorie is simply another unit for measuring work and energy, and not heat alone.
At this poi nt we must want the student not to consider heat as a new or diller
ent fonn of energy. It is just a name given to a special form of work or energy
t ransfer in which a very lnrge number of partieies participate. Before the concepts
of interactions and of the atomic structure of matter were clearly understood,
physicist!! hnd classified energy into two groups: mechanical energy, corresponding
to kinetic and gravitational potential energy, and 1l0nnrechallical energy, divided
into heat, chemical energy, electrical energy, radiation , etc. This division is no
longer justified. Nowadays physicista recognize only kinetic and !>otential energy,
with potential energy being denoted by a different expression depending on the
nature of the eorresl>onding physical interaction, and with heat and rndiation be-
ing expressions of two mechanisms of energy transfer. Chemical energy is just a
macroscopic term used to describe energy associated with electrical interactions in
atoms and molecules, energy which manifest!! itself ill chemical processcs; that is,
as atomic rearrangements in molecules.
,
1"1.5) The {v,/Iow o/lhumodYlI(lmiu 467
11.5 Th e " 'irst La." of Thf'rmodYllollllc Jf
In the previous two sections we have 800n that, when we are dealing with systems
composed of a very large number of particles, we should express lhe WlaJ. eztr1Ial
tcOTk as
. the sum of two ... "rts Q + IVu~. I'.erc IVu~ expresses the external work
.~.
\\'he~ It can be computed as an avcragc force timcs a d istance, as discussed in
Section 11.. 3, and ~ rcpn:sents the ~ternal work when it must be expressed as
h.eat, as diSCUssed III SectIon 11.4. bquation (11.4) for the principle of conserva-
tion of energy must then be written in the form
U- UO=Q + lVUI, (J 1.11 )
which may be expressed in words by saying that
the change of illternal energy 0/ a .syslem i.s equal 10 lhe heal oosorbd
1Jlm the e.rter7lai work dmle 011 IIle .sys/em.
Equiltion (11. 11) call ~ sccn pictorially in Fig. 11- 2(n): Heat Q is absorbd by the
system und work lVulls dO'le 011 the systclll. Their SUIll Q + lV. x1 is stored as inter-
n.ul energy U - U? of the system. Sometimes, especially in engineering applica-
tions, we do nOt. wnte the external work lVu , done OIL the systcm, but the externnl
work IV done by the system; as cXI>lained before, this is the negative of the work
done on the system. Setting IVu l = - IV, we hnve, instead of &t. ( 11.11),
U- Uo=Q - IV. (J 1.1 Z)
E(luat~on (1 1.12) is illustrated ill Fig. 1l- 2(b): Heat Q is OOll)rbed by the system
work IV IS done by the system, and the difference Q - IV is .stored as internal energ):
U - U 0 of the system.
(.1 ft.)
Fig. 11-2. Relation between heat, work, and internal energy.
The statements related to Eqs. ( 11 . 11 ) Ilnd (11.1 2) constitute what is called the
first law of tltern.wdynamic.s, Ilnd is simply the law of conscrvation of energy applied
to s'ystems h~v.l!Ig n very large number of particles, with the external work con-
velllelltiy split m10 t\\"o statistical tc rmfl, olle still called work and the other called
heat.
We may nole that because of its definition, lite inter7wi energy oj a system depends
olily 011 the slate oj the system, whether or not it is in equilibrium, and it. does not
?cpcnd on how t~~ s~'steOi reached that state. However, only when the system is
In n state of eqUIlibrIUm and the particles composing the system obey :'Ilaxwel1-
...

r 11.6) 469

4" Th~,.modynamiu
(11.5
Boltzmann stntistics can Eq. (10.24) be used to compute Uj that is,
, d (
U = kNT dT JnZ).
On the other hand, tne work IV and the heat Q are quantities directly related to
the process that the system experiences whell it goes from the initial to the final
statc. T hat is, when the system goes from a given init ial state to a given final state,
several processes mllY be possible. For fl.l! the processes connecting the same states,
the values U o and U of the initial and finnl internal energy Me the same, so that
the difference (J. U = U - U o is independent of the ])rQCcSS. But the values of the
heat Q and the work IV in general are dilTcrcut for each process. In other wo rds,
the division of the energy exchange into heat and wo rk depends on the process.
An especially interesting case occurs when the system undergoes a cyclical
iralla/ormation, or simply a cycle. T his ml!ans that at the end of the prQCC!S8 the
system returns to iUl initial state. Therefore
u= uo and tJ.u = U - U o = 0,
11.6 Graphical IfeprelU!ninilon 01 '1'fH!#!1UW1f
T o describe macroscopically the staw of equilibrium of a system of atoms or mol-
ecules, we usc some macroscopic or statistical parameters. T he most usual ones
are the pressure, the temperature, and the volume. We could also usc the total
intcrnal energy, but this is not common. If the system is composed of two or more
independent substances, in order to complewly specify the state of the system, we
must also know their relative proportions.
T he macroscopic or statistical variables describing the state of a system in
equilibrium are not all independent ; t hey are related by a mathematical expression
called the equation 0/ slale, which is characteristic of the physical structure of the
systcm. For example, the eqUation of state of an ideal gas (sec Section 12.2) is
pV = NR T, (11.1 6)
where N is the number of moles and R is the gas constant defined in Eq. (10.43).
One of the most important problems of statistical physics is to derive the equa-
tions of state for different kinds of substances, since a knowledge of the equation
of state is of immense theoretical and practical importance.

which, whcn substituted in Eq. (11.12), yields r

Q = IV. (11.13)

Thus in a cycle the heat Q absorbed by the system is all trnnsfonned into work lV /{p, v, T)-O
done by the system. This is just the operating principle of thennal engines, whose
purpose is to absorb heat and perform work in a cyclical fwshion.
If the transformation suffered by a system is infinitesimal, we must replace
tJ.U = U - U o by dU, Q by dQ, and IV by dlV in Eq. (11.1 2). When we do this,
we obtain the following expression : 1 /' / 1_ _ _
... ~" 1 ,, ______ V
dU = dQ - dlV. (11.14) t " """_ I ,,"
- -I:. ---. I,

This equation expresses the first law of thermodynamics in differential foml.

, ..
I
Proj""tion
of trllnsformation
to .....
B

Kote that we are writing dQ and dlV and not dQ and dlV for the infinitesimal on po l' plAne Fig. 11-3 . Thermodynamic surface.
changes in Q and IV. The reason we do this is to emphasize that, although U is
a function of the stMe and its change depends only on the initial and final states,
Q and lV are quantities associated only with processes. In IllalhematicalJ.lnguage, Let US dcsignate the equation of state of a single homogeneous substance by
we S:l.y that dU is all e)(act differential of the variables used to define the state of /(p, V, T) = O. We may represent this function by a surface called a thermo-
dynamic tur/au, using a set of axes labeled p, V, and T (Fig. 11-3). A particular
the system, while dQ and dlV are not.
When the work dll' is due to an expansion or change in volume, we have from equilibrium slate of a system, characwrizcd by certain values of p, V, and T, is
represented by a point S on t he surface. If the syswm undergoes a process or t rans--
Eq. (11.8) thatdlV = pdl', and Eq. (11.1 -1) becomes
fo rmation it eventually passes to another equilibrium state S', also on the surface.
dU = dQ - pdY.
(lI.IS) I n general, the intermediate states occupied in the t ransformation S -+ S' are not
equilibrium states and cannot be re presented by points on the surface
But we warn the student that there may be other kinds of work in additiOll to
expansion, yiclding different expressions in terms of the variables of the problem. / (p, V, T) = O.
For example, if a charge dq is moved by emf l't, we must write dlV = V t dq.
 '70 Thermodyn(JltlU:'
,b, ,,'
Fig. 11 -4. Reversible c:.:pansion and oompression of a gas.
However, if the trnnsforlllntiOll occurs yc ry !Slowly (proceeding at all times by
infinitesimul steps, so that at each stcl) the system is only slightly disturbed r r~1II
its stale of equilibrium), we may r<:l\$Onn.bly assume that the system nl each In-
stant is ill stltlisticni equilibrium. A trnnsfonllation of this kind is !Snid to be
rel'trlible.
We mny usc the expansion of a gas to illustrate a reversible transformation.
Suppose that the pistoll in Fig. 11-4 is held in I>osition by many ISmail weights, ~
indicated in Fig. 11-4(a), At txluilibrium the pressure of lhe compressed gas IS
equ:l.l to the pn'Siure due to the weights plus the atmospheric pressure. If we re-
move one of the weights, by sliding it. to one side onto a platform, the cx~ernal
prc!<Sure decreases by a s1llall amount and the e~uilibri~m o~ .th~ gas. is sl~ghtly
di,,;turbed. T he g.'I-'l then undergoes a 8111all expnnslOlI until eqUlhbrmm IS (qUIckly)
restored. When the process is repeated a number of times, the gas eventually
expand~ up to the volume sho ..... n in (b) and the weigh!..':!, which were previously on
top of the piston, arc s tored as shown. Since the process ~as oce~L r~e<1 very, ~lo~'ly,
we Inay nssume tha t the gas 11M remained continuously III staUslLcal.e~I~lhbr1um
and that the cxpansion has becn reversible, To restore the gas to the IIlltml state,
all we ha\'e to do is to place back, in the reverse order, the same weigh!..':! we took
off, At the end the gas is in its initial state, having completed a cycle, and no
change hM been produced in the surroundings. In other words, in a cycle entirely
com/loud of ,.ef~rlJible trims/ormations, it i8 pouible to arrange thill!!' so that 110 00-
serrable clJallye ill 11,.oduced either ililhe '!1$lem or ill the rurrOUlldillY', . tion from state ,4 with pressure PI :lIId volume F I to stute B with 1)I"CSSUre 1'2 and
On the other hand, an irret'ersible process occurs when the system devul.tes to a
great extent from the equilibrium state. During the process such statistical quan-
tities as pressure and temperature are undefined. Eventually, a.t. I..he end of the
l)roce$S, the systcm rcturns to e(luilibriuLiI in a new statc ch:\ractcrL7.ed by :l cer-
tain pressure and tcmperature. In general, irreversible processes occur at. greaL
speed . We may again usc the expansion of II gas to il1lLst ~ll.tc an ir~versible p~ocess.
The g.'l.8 in Fig, 11- 5(11.) is as it Wfil:L in Fig. 11 -4(11.), but wLth nil weIghts CQnsohdated
into one, bbclcd A, ?\ote that there is also 3. weight B at the upper level. If
\ ..
(11.6
- 11 ,6) Graphical rrpru<'IItation of prottllU
"
,., 11 ,,'
Fig, 11-5, Irreversible expllo<ion Hnd compreJilion of Il gM,
weight. A is $uddellly rcmoved , the external pressure suddenly drops und the
gas expands rapidly, with It great. turbulence in its molecular motion; i.e., the
proccss is irreversible. During the process Ihe moleculilr velocities do not follow
the i\1axwell-Boltzmann distribution lull'. Finally the piston comes to rest at n
certnin position and eventually equilibriulll is restored, with well-defined pressure
and temperature, as indieate<1 in l-'ig, I I-J(b), To take the gll.S back to its initial
state, we may move weight B to the tO I) of the piston, which then movC9 down in
a process which mayor may not repeal, in reverse, the previous process, In the
end, when equilibrium is once more restored, the g3.'l is again in its initial state,
I\lj shown ill Fig, 11-5(e); the gas has completed u cycle. I-I owever, a definite
change has occurred in the surroundings, Weight B, which IIIlS initially at the top,
is now :~t the bottom. Thus: I n a c!1cle composed, ill llarl or jll /o/.al, 0/ irret'ertsible
traIl8/ormatioll8, the s!1stem retUl'll8 to its illitial state, but a jilOite measurable change
is woduced ill the sWIoululillI/8.
It is clear that a reversible lnmsformatioll can be rep rescnted by n line 011 t he
thermodynamic surface f(,1, V, 7') .", 0, joining the initial and fin:11 slates Sand
S', but:\n irrc versible process Clmnot be represented in slLch a way.
The three l)arameteTl< p, V, and 7' a rc not indcl>cndent, since they are related by
the (.'qmltion of state /(11, I ', T) .", O. Therefore in geneml it is neces.."lI.Ty to use
only two coordi nates to rel)rcscnt a givcn process. A common case, especially for
ga.'lCt", is to usc a p-I' diagmm. For exnmple, in Fig. II- G, a rcven!ible tnlllsfomla-
volume 1'2 is represented in a p-I' diagram. The temperature ilL each instant is
obtain(.'ti from the equation of state. The p-I' diagr.Hll is c:<pccially useful for
ga.'lCou~ procC8/SCS becausc the.\' beur a du~c relationship to the \lork done by the
ga;;. HCC:lllilig Eq. (J J.i), we nute that p (/1' is the area of n ~trip of width !IV and
height 1', llnd therefore the work dtJlLe by thl! I'ystcm in g'Jing from A to B by a
ccrlliin process is given by
11' A_II = /, "''P dl' .
",
 -
(11.6 11.7) 473
Thumodynamicf

, , 011 the systcm. The net work IV done by the systcm during the cycle is thus the
A shaded arca enclosed within the curve reprcscntiug the cycle; that is,

IVcrde = f P dV = area undcr (I) - area under (2) = area within A(I )B(2)A,

,I ,
8(1"f, V 2)
,,8 As indicated in Scetioll 11.5, thcnnal machincs do work at the cxpense of heat ab-

"I,, ,, sorbed in a cyclic.'.l process. The work done per cycle, if the process is reversible,

,, ,, can be com puted once we know the p-V dbgram of the cyclc. T his work is also

I
I" ,, equal to t he net hcat absorbed by thc system during the cycle.

dV v, V 0 V II.? Sperilll Proce8Hf!1I

0 V,

Fig. 11-6. Diagram of a reversible pro- Fig. U-7. The work done in going from Let us consider some s pecial processes, limiting ourselvcs to the cn.sc in which the
ce!!8 in the p- V plane. The work done by the state A to state B depends on the process work is due to expansion only, Then E<I. (11.15) holds for an infinitesimal process.
system is indicated by the shaded area. followed by the system. That is, dU = dQ - p d l'. An isoc.horic trails/orilla/ion is one in which the volume
remains constnnt. T hen dlf = 0 and Eq. (ll.l ;j) reduecs to

The work done is then the area under the curve AB in Fig: 1 ~...u, co~responding to
the t ransformation. T his hclps us understand what was said In Section 11.5 abo ut
the work depending on the process. Figure 11- 7 indicates several processes, cor-
responding to curves (1), (2), and (3), al ~ of. which take a system f~om state A to
state B. Since the area undcr each curve lS different, the work done III each process
is also different. The initial and final states are the same for the th~ processes,
and thus the change tJ.U = UA - U B in internal energy is the same III each .case.
Therefore the heat corresponding to each process, given by Q = .tJ. U + W ,. w,1I be
differen t. If the process is irreversible, it cannot be represented III a p-V diagram,
and the calculation of the work is more difficult. . heat absorbed, which is to be expected because there is 110 extcrnalwork.
Let us next consider a cycle, in which the sylitem goes from A to B (Fig. 11- 8)
along process (I) and returns from B to A along process (2). In going from A to
B it does a work equal to the area under curve (1). In returning from B ~ A it
does a work equal to the negative of the area under curve (2) because work lS done
If = COllst, ( 11.17)
whcre the subscript V is used to emphasi1.c thnt this cquiltion holds only Ilt con-
stant volume. For a finite tmnsfornmtion \\e havc, integrating Eq. (I L17) (or
from Eq. 11.12 with II' = 0),
l' = const.
So, in nil isochoric trans.formation, the change in inlemal cncrgy is equal to t he
Let us now introduce the conccpt of heat capacity al cOlis/ant rolume CI', which
is equal to the heat absorbed by one mole of the su~tftnce per un it change of
temperature, at constant volume. T hus we can usc &,. (11.17) and obtain

, CV=.!.dQV=.!.(au)
NdT NiJT ,
.
1
(11.1 8)
. / -. . (1)
., where N is the number of moles in thc system. In eilicubting aU/aT, we nHlst
indicate that J' is constant, since wc may also ch:H1ge thc tcnlperature in other
ways, resulting in a ditTerent way of changing Ihe intcrnal cnergy. In general,
the heat capllCity C 1' is not constant, but v!\riell wilh the tcml}CrHturc. Since it is
':::-_ _.-;8 n characteristic of each substance, it is lIll ill1portant rnncroscopic or statistical
(2) quantity.
An isobaric transformation is onc in which the pTCi;Sure !cmaiILS constant, Then
Fig. 11-8. Cycle. The work done b~ t~e dp = 0 and wc may substitute (p I' ) for p dl'. Introducing this rebtiOl1 ill
system in describing the cycle clockWise IS Eq. (11.1 5), we have
equal to the area enclosed by the cycle in a
1'""" V diagram.
o v, V, V Jl ... COllsl,
 po

'" Thermodynamics (11.7 11.8) Entropy Ilnd the secQnd law oj thermodynamic.,
'"
where the subscript p serves to emphasize thai the equation holds only nt constant 11.11 Entropy and the &>confl ' Jult! 01 Th e rmodynamics
pressure. Thus Til Cha!)ter 10 we .obtained the equilibrium !)artilion of a system, which depends on
p = canst, the pr.opertics .of the c.omponents of the system and e.orresponds to the most prob-
(1 1.19) able distribution of the molecules .of the system among the dilTerent available
whe re the quantity energy st-ntes. Under such conditions P (or In P) is a maximum. If the system, al
though isolated, is not in equilibrium, we may assume that it is in a partition (or
H =U+ pV (1 1. 20) distribution) of lower probabilit.y than the ma.ximum .or equilibrium. In due time
it will evolve, under the interactions among its components or molecules, until it
is called the enthalpy of the system. For a finite transformation, we have, integrat-
aUains the partitiQn of maximum probability. At this time the system reaches
ing Eq. (11.19), statistical equilibrium and no further increase in P (or In P) is expected, unless the
p = const. (1 1.21) system is perturbed by an external action.
To describe this natural trend tOll'ard statistical equilibrium by evolving toward
So, in an isobaric transformation, the change in enthalpy is equal to the heat ab- the partition of maximum probllbility, the im!)Ortant concept of entropy, S, has
sorbed. T he work done in an isobaric transformation, according to Eq. (11.9), is been invented. Entropy is defined as
(11.22)
s= kIn P, (11.25)
T he heat capacity at COI!slollt pressure, C,,' is defined as the heat absorbed by one
mole of the substance per unit change of temperature at constant pressure. Thus where the Boltzmann constant k is i[ltro<iuced for convenience in writing future
mathematical expressions. Thus Ihe entropy of a system is proporliotlalto the loga--
C _.!. dQp _l. ('H). Titllll~ of Ihe probability P of the parlilio/[ corl'esponding {o tlie slate of tI~ system.
(1 1.23)
P - N dT - N aT " This definition .of entropy ap!)lics to any partitiQn or state, either .of equilibrium or
nonequilibrium; this is in c.ontrast tQ tempcmture, which is defined only for equi.
Kate that both heat capacities C" and CIf arc expressed in J 01(-1 mole- 1 in the librium partitions or states. T his definition also me;l!lS that the entropy of a
i\U':::SC system of units. However, it is customary to use the altenHl.tive unit system is a prQperty .of the state of the system and theref.ore
cal C- 1 mole-I. The average heat capacity of water at constant. atmospheric
pressure is 18.00 cal C- 1 mole-I. H istorically, the calorie was first dcfined as llie ehallge in elltropy of a system u:hcl! it goes from one siale to aM/iJer
ihe energy rcquired to incrcase the temperature of one gram of watcr (or n
mole) is indepel[dellt of IIle process folIO!~'ed,
by 1C at constant preSl:;ure.
An iBothermal/ranBformation is one in which the temperature does not change. sillce it is determined by the probabilities of the initial and final partitions. For
For an ideal gas, whose internal energy U = tNRT depends only on the tempera equilibrium states, the entropy can obviously be exprcssed as u function of the
ture, the internal energy doc~ not change in an isothermal process; that is, dUT = O. macroscopic variables defining the sWlte. A reversible transformation of !l. system,
T hus Eq. (11.14) gives isolated or not, in which the entropy of the system does not. change, is called an
iBelilropic transfQrmation.
dQT = dW T 0' QT = II'r, for an ideal gas only. When we have t\\'o systems with probabilities PI and P 2 , the total probability
.of the partition resulting from the c.ombination of the two systems is P = P1P2'
T his relation, we rcpeat, is valid only for the isothcrmal transformation of aL\ ideal Thus 111 P = In PI + In P 2 and S = kin P = k In PI +
k In P 2 = 8 1 +
S2' We
gM. see then that entropy is an additive quantity. T his is one of the reasons why the
An adiabalic Imllsfol'mation is one in which the system neither absorbs nor gives concep~ of entropy is more convenient to handle than the concept of probability.
up heat. T hen dQ" = 0, and Eq. (11.l4) gives }(ceping in mind .our definition of S and recalling from SeetiQn 10.2 that the
(11.24) state .of statistical equilibrium corresponds to the most probable partition, we
dU a = - d lV.. ,
conclude that the entropy of an isolated system in statistical equilibrium has the
where the subscript a stands for adiabatic. Expression (11.24) indicates that in maximum value compatible with the physical e.onditi.ons of the system. Hence the
an adiabatic transformation the work is done at the expense of the internal energy only processes that may occur in the isolated system after it reaches statistical
of the system. Thus the temperature of an ideal gas (and of most substances) equilibrium are thQSC p?ocesses that are compatible with the requirement that thc
must. decrease during an adillbatic expansion and increase during a[\ adiabatic entr.oPy does not change; that is, dS = O. T hese are obviously reversible processes,
compression. because the isolated system is in equilibrium. On the other hand, if all isolated sys

\
 - .,

(11.8 11.8) Entropy and !he uCOlld /aU! oj !hermodynwnia

47. ThumodynamiCl

teill i8 not ill equilibrium, it tvillnaturally eoolve in the direction in u:hich il8 Im/rOI)Y
"'"
j'lcrt(l8e'. since these arc the processes that carry the system toward the state of
maJ[imulIl probability or stntisticnl equilibrium. Thus the processes that arc morc
likely to occur ill nn isolated system nre those ror which

ciS ii:, Oi (11.20)

the inequality holds when the isolflted system is not initially in equilibrium, and
the processes arc irrcvel'l'Jibic.
We may thell state the ucond ta ll) oj Ihermodynamic8llS follows:
1'he moIL 7Jrcbab1e Pl"/XCBUIJ that may occur in an 180Wted 8y81em art
, thou in ldtich llu) entropy tililer increase8 or remaills cOlis/aut.
This statement must be illtcq>rctcd in a statistical sense since, in a pll.rlicuhr in-
stance due to the fluctuations in the molecular distribution, the entropy of an
isolated system may decrease, but the larger the decrease the less likely it is t~
occur. The variation of entropy during the evolution of the system towurd eqUI-
librium may t.hus be represented by t.he irregular line in Fig. 11- 9.
Fig. 11- 10, Irrevel'llible diffusion of ink in water.
extremely improbable occurrence, and so fa.r has never been observed. On the
other hand, there may be small fluctuations in the concentration of ink molecules
at different places, even a.fter equilibrium has been reached. But these fluc tua-
tions, in most cases, a.re not noticeable.
If a system is not isolated, its entropy may decrease by interaction with other
systems, whose entropy must then also change. But the total a.mount of all changes
of entropy made by all systems involved in thc l)roccSll must be in agreement with
EQ. (11.26), with dS = 0 holding fo r a reversible l)rOCeSS and dS > 0 for an
irreversible process.
I~o r example, if a combination of two systems is isolated and lhe lotal entropy
is S = Sl + S2, the processes occurring in the combined system must satisfy

dS = ciS l + (lS2 iii:. O.

Fig. 11-9. Variation of entropy of
an isolated system while the system ~
evolving toward equilibrium.
Ti ....., I
The second law of thenllodYllamics expresses the well-known fnct. that in an
isobted syst.cm there is a well-defined trend or direction of occurren~e of processes,
and this trend is determined by the direction in which the entropy mcreases,
Transport phenomena, such as molecular diffusion and thermal conduction, are
good examples of processes that always take place in one dircc~ion .. In both cases
it lIlay be verified that the entropy of the system increases. DIffUSIon tak.es p.bee
in the direction in which the concenlration tends to be equalized, resuitmg m a
homogcncous systcm. T he reverse process, a spontaneous change of a hO~\logencous
system into a nonhomogeneous system, which corresponds to a decre~e m c.nt~opy,
is nevcr observed. For example, if fl drop of ink is released at a pomt A mSlde Z1.
vessel filled with water (Fig. II- lOu), the ink molecules spread q\lickly throughout
the water find after some lime the WZ1.ter is unifonllly colored (Fig. l l- lOe). In
this proce~ the entropy of the system has increased. However,. if at a given timc
the velocities of all the molecules were exactly reversed, all the mk would eventu-
ally collect back at A , resulting in a decrease in entropy. Bul. this is obviously an
The entropy of one of the components may decrease during a process, but the net
change of entropy for the whole system must be positive or zero.
The great importance of the second law of thermodynamics, as expressed by
Eq. (11.26), is that. it indicates those processes which are more likely to occur in
the universe as a whole. Therefore there are many processes that could occur
because they comply with other laws, such as the conservation of energy, How-
ever, it is very improbable that they will occur, because they violate the second
law, or requirement (1 1.26).
EXAM PLE 11 .3. Entropy of a eystem in statistical equilibrium and which obeys
Maxwcll-Boltzmann slatistiCl!.
SolraiQll: Recalling expression (10.[3) for In P in Maxwell-Boltzmann statisticS, and
recalling that N - LI Ili, we have
S - klnP - k[Ltnllngi - Ltnilnnl+ Ltlli]
-k L II; In (rlj!gl) + "N. (1 1.27)
 po

(11.8 11 .8) En/ropy 111ld /he second laID o/Inumodynamict

But from Eq. (10.23) we have

.
. ...... .
>//.......::'. ,,
II, -
N
Z",C
_K;/tT
. ,
... ;. Y .:::::-:;
.. ':. v .2V:
...:: ....
Taking the logarithm of thb equation, we have .:.:
"II; f;; Z
In - - - - - I u - 2 2
g, ~'T N Figure II- II
ThUll Eq. (I] .2i) becomes
alit)' of irreversible processes, ~ause, as ...... e see when we look at Fig. II - II, if the gas is
initially in container 1 and by some means (such as removing the \\'all w) it is allo ...... ed to
expand freely into container 2, in a 8hor~ time the molecules of the gas sre di$tributed
over the combined volumes of 1+2. Ho . . . el'er, no one expects that at a certain laler
time, 11..'1 a l'e!Iult of the molecular motions, all molecules of the gas will appear concen-
trated back in container r. Thi$ proceS!! is possible but highly improbable. Thus the
free-expansion procegs V .-, 2V occurs ill nature, but the reverse process docs IlOt. Ac-
J[ W() 11011' recall Eqs. (i0.1) and (10.2), we finally get cording to the second law of thermodynamics, the first must correspond to a n increase in
entropy of the gas and the second to a clecreMC.
U Z U ZN Let us 110'" proceed 10 compute the change in entropy. The entropy of the gas in the
(11.28)
S - r + kNln;V +k.V - T+klnN!' first state is

f: XA MI'I.J.; 11.1. EntrollY of 1111 ideal gas in slati31ieal equilibrium.

Once equilibrium is re established, alld the volume is doubled, tbe elltropy i$
Solul io .. ; We know that, for an ideal gas, U - jkN7', and in &t. (10.40) we obu.inoo
the partition function of an ideal gas as S2 - "N In (2"T3r.1) + So.
z _ 1'(2r mkT)3/2 The temperature bas not varied ~ause the average kinetic energy of the molecules of
h' the ideo.l gal! ha.s not changed. The molecul~ only mO\'e in a larger space. The change of
entropy in the process is therefore
i\ [nkillg the substitutions in Elt. (11.28), we obtain
( 11.30)
1'(2rmkT)3 /2
S _ ikN+k.Vln h 3N . So the (irrel'crsible) proceSl!, which is one that certainly occurs in nalure, produces an
increase in the entropy of the ga.s.
This l'e!Iult is known &.'i the S/lCkur-TelrlXlc tq"lIo(um. It can be written in the alternative lIowel'er, the re\'l~rse procC$l, in wh ich we ail1!ume that the gas initially occupies the
whole container (or volume 21'), and then at a certain later lime occupies only tbe volume
form
(11.2'9) I' at the left, corre:::ponds to a decrease in entropy; that is,

AS' - SI - S':: - - k.l., In 2 < O. (1 1.3 1)

where /I _ V I N is the volume IJoer molecule and all qunntities that are not \'ariables ha\'e
been inchlded in So; that is,
t;X ,IMI'U;; " .,;. The change of entropy of au ideal gas durin g a free e);pan~ioll.
501,,/;0., ; When a vessel containing a ga~ i~ eoune<:led with nn empty \'~I, the gas
unde .....;~ a /r(c npamum. Such a proce>lS is irrCl'cn;ible, and equilibrium i~ des~~yed. for
a certain time until the final Slate is achieved. Thi.::! is al;;o a ll e~ample of the umdu'ectll)ll-
Thus thi~ proce...~, although possible, is very unlikely to occur naturally if the gas is
isolllotcd. It i~ true tha t we may compress the gas i;;othermally, reducing i t~ volume from
2V to V, with a corrCSI)Qnding decreMC in entropy equ31 to lhe value given by Eq. (11 .31).
But this requires an external action, nlld it is thcl) ncccss.ary to take the eliternaJ changes
of entropy into account to obtllill lhe lOla/ change in cntropy in the universe.
It is instruct ive to look at the same situation from a probabilistic point of view. From
definition (11.25), wc h.'l\'e th3t
p,
- kin-=-
p,

' 80 Thermodyn(lmiC! (11 .9 /1 .9) Ell/ropy alld IIw/ 481

When we compare this with Eq. (11.30), we have

P,
expansion of a gas, the changc in energy EIII; dE;
is due to the change in the dimensions or volume e, ,,,I
Inpl _ Nln2 _ In"Ji
-N P: _ '},'"
P, . of the contniner, and thus corresponds to what
we h3ve cn.lled work. Reca\[ing Eq. (1 1.1 4),
_r e, ,,
.,
-------- -------- ,
In general, the number IV of molecules of the gas is \"ery large and hence P2 is much dU = dQ - dW, we conclude that the work done , ,,
greater than P l. This account.8 for the ra pid rue at wh ich the gas cxpande freely UI) to by the system is
the volume 2V. For the reverlle process, 2V _ V, we get PL / P2 _ 2- N, and this is an
extremely ~mall quantity for the number N of molecules that arc usually found in any = - 2: R;dE;. ,,I
sample of gas. Hence it is extremely improbable (although IlOS8ihle) that at a certain
dW ( 11.33)
,
time all the gas molecules, as a rellult of their interactions, appear concentrated again in
the region V at the left. or course, for a very small number of mQiecuies (N _ 1 or 2, Equation ( 11.33) gives the work done by the sys- ,,,I
for example), we have P dP~ - i or t, a nd it is possible in a short time to observe "all" tem in terms of the change in the energy ievels, ,,
the molecules (one or two) on the left-hand side. But then, of course, statistical methods resulting, for example, frOI1l a change in volume. ., ,
.,,,
E
T his puts the statistical defi nition of the wo rk
are unneees.'!Ary, and have no meaning, and it may be even possible to calculate the exact
t imes at lIhieh the particle or the two particles will be on one side or the other. done by a system on a firmer b.'lSis than it was ill --------._t'_K,
------- -
,,
our preliminnry definition, given in Section 11.3. ,,
11. 9 Entropy and IIe a t
Dy introducing Eqs. (11.32) 3nd (l1.33) into ,,
dU = dQ - dW, we conclude that wc must write ,,
We must no\\" see hOI\" entropy is related to the other thermodynamic quantities
2: Eldn; E, dK 2 ,
we have previously introduced. Suppose that a system in statistical equilibrium dQ = (11.34) ---- -i,
,
undergoes an infinitesillla\ transformation as a result of its interaction with its
surroundings. The intcrnction results in a change of the partition numbers n, and fo r the hca~ absorbed by the system. That is, E , dE, ,
of the possible energy states 8 1. Since U "'"' LlnIE wc then have that
the statistical quantity lI"e have defined M heat is
" a changc in energy of thc system due to molccular
(1l .32) jumps betwccn cnergy levcls resulting from energy Fig. 11- 12. Change in energy
le,cls of a IXltcnlial box when
exchanges with the surroundings, a result in Ihe width of the box L, changed.
This equation holds whether the process is reversible or not. However, we shall essential agreemcnt with our previous definition
limit ourselves ill this section only to reveraible transformations, so that at each of hcat in Section 11.4.
instant the systcm is essentially in statistical equilibrium. The process must then D uring a reversible process, there is an important rclation betwccn the change
be slow enough so that at each instant the distribution of the molecules cnn ad- in entropy, the heat absorbed, and the absolute temperature. T his relation is
just to the corresponding most-probable partition.
dQ
Examining Eq. (11.32), we note that. the first sum, E, E, dnl, corresponds to a dS=r' fo r a reversible process only. (I 1.35)
change in internal energy due to a redistribution of the moleeules among the
available energy levels, while the second sum, E, n; dE;, corresponds to a change It is !l. direct consequcncc of the definitions (11.25) for entropy and ( 11.34) for the
in internal encrgy due to a change in t.hc energy levels. Let. us examine this second hent nbsorbed. The proof is given in Example 11.6. Rebtion (J 1.35) indicates that
tern1 first. In Section 2.5 we diseussed the stationary states of a particle in n. one- entropy is expressed in J oK-lor in cal 0].;:-1, which was implicit in our defmition
dimensional potential box of width a, and we found that the cnergy levels are (11.25), in view of the uniu of k.
given by Frelll Eq. ( 11.3.) we have dQ = T dS, which may be incorporated into
Eq. (1 1.1 4), giving, for a reversible process,

dU = TdS - d lV. (11.36)

If the width a is changed by the amountda, the encrgy levels suITer a corresponding
Whcn only expansion work is done, the preceding relation ~omes
change dE~, as indicated in Fig. 11-12. A similar change in the energy levels will
also happen in a 3-dimcnsional potential box of any shape. So, for the case of the dU = TdS - pd l', (11.37)
 ...
Thmnodyrwmiu ( 11.9 11.9) Ell/ropy and ~/ 483

which Clq )rcsscs t he change in internal energy during a reversible process in te rms
of the changes in entropy and volume. Again we state that Eq. ( 11.14) is uni-
versnlly valid, while EllS. (11 .36) and (11.37) can be used only for reversible
proccsscs.
From Eq. (11.37), if the volume is constant, dU v = T !lS I' or
I f "I is larger than 113 by at least 2 unit!! (in general, "I is much larger than 113), we have
that 1" is larger than P. lIenee we conclude, in general, that P incrca~ with the energy
U, IlL constant Iolume. Of course it i~ ]"IOl!Sible that under certain circumstances the
part ition IIT0babilit y does not changc, or it may evcn dccrease when the total energy
inc rcllSC~. In lJaT\ icular, whcn the particles of a system hal"e only a limitcd (or finite)
number of aeccssiblc Sla tes, it may be shown that P may be a decrcasiug fun ction of the

T1 = (as) ,
au ,,= k au (In Ph-
cncrgy for certain ellcrgy ranges. This would result in a nega lh'e ab!IQlute tcmpcraturo
at such cncrgies (see Problem 11.(7).

I t can be shown that, in gene ral, P is all increasing function of the energy of the f.X /IM/J U~ 11.6. Derh'al ion of I~<.J. (1 1.35) for the re lation betwecn the change of en-
system; that is, the larger the energy, the large r the partition I)robability P , so tropy and the heal absorbed by s systcm in a rel'ersible transformstion.
long 11..9 the volume remains the same. H ence, for such systems, the absolute tem- So/ulio", Let us suppo..<e that our lIy~lc m obeys .\Iaxwell-Bolt~mann alat istic!!, an
perature T is a positive quantity. For that reason T = 0 is called the absolute a ulllption of wide validilY. Theil the cntropy for an equilibrium state is given by
zero, since in such cases there can be no temperature below thn~ vnlue. I':q. (11.28); that is,
Histori cnl1y, the concept of entropy was developed in ph ysics in nn o rd er oppo-
u z
site to that of our discussion. The convenience of the rellltion dQIT for several S - T+ kN In i; + kN.
th ermodY llluni c cnlculations was reeogni1.cd by Kelvin, C lausius, lind othel"l:! dur-
ing the middle of the ninetccnth centu ry. I n 1865 Clausius introduced th e name For an infinitesimal re\'crsible tran ~for mation ill which the total numbcr of parti clcs
til/rOIly to designate a qUflntity whose change during a reversible l)tOCCss was given doc~not chauge,
by Eq. ( 11.3:)); th aI is, liS = dQ/7'. T he relntioll between entropy, 11..9 defined by
ClaU!;ius, a nd the probability of a partition, as given by Eq. (I 1.25), S = kI n P, tiS _ dU ~.!!..dT + kVdZ, (11.381
T T2 . Z
was first stated by Ludwig Boltzmann in 1877. Once [he Illoiceulll.r approach to
thennodynamie processes WII..9 recognized 11..9 more fundamental , the Boltzmann !ince d(ln Z) - dZ/ Z. ltecalliL\g the dcfiuition (10.22) for the partition function in
d efinition of entropy, instead of Clausius' d efinition, became more relevant from .\[axwell-Bohzmann statist ic~, Z _ L. Q,,-F.;/iT, we hal'e that
the theoretical point of view.
dZ _ ~ " dE; -~,:iT+ " ..!i!. -1!,;iT
~ kT Q;' L..J kT'l Q,e dT .
, ,
Note 0" tile $;8" of til e absolute f.emIHlr!tture
We may analyze the variation of the probability P with the total energy U a.t constant Then, using Eq. (10.25), II'e may writc
volume in all intuitive way as follows: Suppose t hat the system of particles is enclosed
in a box of fixed volume. Then the pOl3S.ible energy levels are also fixed. lienee, if t.he kN dZ __ .!. " !:!...,.,-Ei,iT db',+...!... " !:!..,.,-8;I.T p ' dT
Z T~
, Z' T 2 L..J
, Z'"
energy of the system i~ to be increased, some particles must be shifted from lower to
hi gher energy levels. Assume that, for a given total energy, the oecUI)ation numbers of
the partition arc ilL, 112, 113, , where III > "2 > rl3 > ... if the system ill in equilib- - - T I", . 1",
L..J "' dt, + 17 L..J ";E. dT -
dll'
T+ U
T2 dT. ( 11.39)
rium. Also assume, for simplicity, that 111 - 112 - 113 _ .. - I . Then the luobability
of lhi! equilibrium partition is
To obtain the last re~ult, we used Eqs. ( 10.2) snd (11.33). SuOOtituting Eq. ( 11.39) in
Eq. ( 11.38), we get

dS _ dU +~ _ dU+dlV.
SUPI)()Se now that the tot.al energy U of the system is increased a.nd that the energy in- T T T
crease ig accomplished by one particle shifting from level EI to level B3. The probability
01 t he ne"' partition is then
ThcLI, since frolll Eq. (II 14) we havc dU + dll" _ dQ, we finally obtain
dQ
dS ~-,
T
Therefore
which i! relation ( 11.35), rclating Ihe change in cntropy and the heat abl!Orbed. We
mUSt keel) in mind that Eq. (11.3S) is I"alid only for s rel'crsible process in view of tbe
fact that our dcril'ation used the cquilibrium pllrtition function.
 po

Thermodynam ics (11.10 11.10) Di$CUSfioll of prOCef stl ill lernu oj t lliropy 485
'"
11.1(' IIillcnNSi(m of l-roct!NlwS in Tt'rllu of F.lltroPII T T

Whell [I system passes frolll stute I to state 2 by menns of u reversible transforma-

AI
, Trllllsformat.ion
A

tion, we have from Eq. ( 11.35) that I ( I)

,I Q
(I I AO)
T"
I
,1 T
,,
A,
(2)
1
gives the change in entropy. The integral on the right-hand !'ide is independent of I 1T 2
the reversible transformation followed when I he system goes from slntc 1 to state 2 ,1 ,
1
because the entropy depends only on the stlltc of the system. Abo t:.S = S2 ~ S I 1 1
depends only on the initi!l! and rimll ~t:,tc.~, but not on the process. 0 S, <IS S, S 0 S
, I n the eMe of an i;,;othcrnml rcvcr.;iblc t ransformation, 7' is cOtlslnn(. and
Fig. ll-13. Diagram of a reversible pro- Fig. 11-14. Cycle. The heat absorbed by
Eq. (1 1.40) becomes
cess ill the T-S plane. The heat absorbed the system in describing the cycle clock-
during the process is given by the shaded wise is equal to the area enclosed by the

I.
82 - SI = V. J2dQ = ~ 0'
area. cycle in a T-S dia.gram.

fo r isother mal processes only. (llAl)

This is a relation of great importance in the rmodynamic calculations. The student
T hus the change S2 - SI i~ positive or ncgutivc depending Oil whether hC!lt is should recognize that the entropy is a variable that may be used to describe a
abso rbed or rejected, !jince T is positive. For nn adiabatic reversible l ransforlnu- process in t.he same way as pressure, volume, or temperature.
lion, since dQ" = 0 , E (I. ( 11 .40 ) gives
EX,IIHPLE 11.7. Thermal efficiency of an engine operating in a Carnot cycle.
0' S = const. ( 11.42)
Solutio", A CorMI cycle is a cycle composed of two isothermal and two adiabatic re-
T hus udinba tic rcvcr:;i ble tnmsfo rnlnlions :Ire at. constnnt entropy, and for that versible transformations. No matter what the working substance is, it is represented by
the rectangle ABC D of F ig. 11- 15, where AB and CD are the isothermal transformations
fC::u;Q1l they are abo isentropic. :'\otc, howcver, that nn adiabatic irreven;iblc
and BC and DA are the adiabat ic or isentropic transformations. The cycle is described
tnl1l~for l11alioll is not llcces;'lrily isentropic.
in a clockwise fashion , as indicated by the arrows. Let us designate the temperatures of
1'rol11 Eq. ( 1l.3.1) wc also have th:lt the tw o isothermal processes by TI and T2, with Tllarger than Tz. During the isothermal
process AB at the higher temperat ure T I , the entropy increases and the system absorbs
Q= f TdS (1 1..l3) an amoun t of heat QL; during the isothermal process CD at the lower temperature Tz,
the entropy decreases and an amoun t of heat Qz is rejected. During the two adiabatic

'- - G
transformations the entropy remains constant and no heat is exchanged with the sur-
givcs the hcat :Ibsorbcd in going from ";\ ,Ilc I \0 state 2 by a reversiblc tr,msforma-
roundi ngs. The changes ill entropy du ring e!u;h T
tion; this integral depends on thc particubr transformation. In fnot, the reversiblc
transforma t ion, according to Eqs. (11.41 ) and T II /j
transformation may be rep resented by a line in a diagram in which the ordinate
corresponds to the temperature T :'I nd the absci;;.~a to theenl ropy S,:lS in Fig. 11- 13. (11.42) re
Then Q is the area under the curve from SI to 8 2. If the tmnsformntion is a cycle 4S,18 _ Qd TI , isothermal, heat absorbed, W_Q
such ns i\( I )B (2) A (Fig. 11- 14), wc thcn have that the change in cntropy is roCI'O, 4S BC - 0, adiabatic,
8 2 - 8 1 = 0, since we return to the initial state, and 4ScQ .. -Q~/ Tz , isothermal, hcat rejected, T~ - jj'
,, ,,, C
adiabat ic. ,, ,,
t:.8 = fd7? = 0, re\'e rsiblc cycle, (11.,1-1)
The net change in cntropy in the cycle is zero, ,, ,,
while the net he:lt :lbsorbcd by the 1:\ystelll in the cycle i~
.,d ,1
,
,1,
o S, So S
Q = j7'd8 = nrc:'l within the cycle in (1', S)-coordill:ltcs
Fig. 11-15. Carnot cycle in a T-S
= work done by the system during the cycle. (11..15) (11.46) diagram.
 po

( // .10
'"
This givClI the re la tion between the heat absorbed and T('jeetcd and the cor responding Suppose now that the substance is initialJy in state A with no magnetic field present,
487

temperature!!. Equation (J 1.46) holds for any suhst:mce that undergoes a Carnot cycle,
whether the su~tance is an ideal gag or not, ~inee "'C have made no 51)ial llllIIumption
about the internal structure of the liub:!tanee. I II the case of a gas, the cycle is atcorn
IJlished by a 6('ries of e)(JlansiOIl~ and compreSllions.
The net heat absorbed by the S}'8tcrn during the cycle is Q - QI - Q2. This is also
equal to the \I'ork II' done by the system during the cycle. Accordiug lo ~:q. (11.'15), we
may write
and that a magnctic field is appl ied i!lOthermally. The substance undergoes lhe trans..
forma~ion l iB. Kext we cut off the magnetie field adiabatically. T hen if the process is
reversible, the entropy does no t change and the system undergoes the transformation Be
ending at point C of cun'e ( I ), corresponding to a temperature T2, much lower than th;
initial temperature T I . If this proce.ss is repeated lMWeral ti mes, a very 10\\' tem perature
may be reached.

On the other hand,

I . ~Th e 1I1icroscopie Interpretation of Entropy,~ D . Frisch, Am. J. Ph!J6. 3-1,1171 (1966)
2. ~ l rreversibmty in Simple Sy81ems,~ A. Hob!lO n, Am. J. 1>h y,. 34, 41 1 (1966)
Therefore the efficiency of a thermal engine operating according to a Carnat cycle (defined
a~ th e ralio of the work done to the heat absorbed al the highest temperature, per cycle) is 3. "A Hundred Years of Entropy, ~ M. Dulla, PhllriC6 Toda y, January 1968, page 75
4. "Concept.'J of Classical Thermodynamics, ~ A. Buchdahl, Am. J. Phll'. 2JJ, 196 (1960)
(1 l.47 ) 5. Staljglu:al Ther-modynamU:I, E. Sehrlkiinger. Cambridge: Cambridge Uni versity Press,
1964, Chapters 3, 4, and 5
Thus we see thaL Iht ~fficie 'lC!J 0/ a I/urmal t ngint oper(lling aceording 10 a rCl'cr~ible CarMI 6. Stati8tical PhY8ic3, G. Wannier. New York: J ohn Wiley, 1966, Part I
elicIt i.s independent 0/ Ihe u;orking subs/alICe and depend& only on the two operating tempera-
7. Fundamemal8 oj Slali8ti<:al ThermodllnamU:I, R. Sonntag and G. Van Wylen. New
lu rC3. This result i~ eommouly kno""n as C(lnlot's theorem.
York: John Wiley, 1966, Chapter 4
Equation (11.47) al!lO sho""! that the absolute temperature must be a positive quantity.
T he rea.!lOlI for t his is that if T2 were negative, then the thermal eflieiency would be grellter 8. The Peynman [_Iureg on Phy,ic" Volume I , It Feyn man, R. Leighton, and 1\1. Sands.
than one (or> 100%), which ig incomllatible wilh the conservation of energy. l3esidc.~ its Reading, Mass.: Addison-WCllley, [963, Chaptcrs 44, 45, and 46
importance in the design of thermal engines, Carnol's theorem shows tha~ a reversible 9. A Source Book in Physic" W. Magie. Cambridge., Mass.: Harvard University Press;
thcrmal engine may be u;!ed as a thcrmometer. For this lJUqlOse it is neces:sary that the page 220 (Ca rnot), page 228 (Clausius), page 236 (Kelvi n), page 262 (Boltzmann)
engine opcrate between a standard temperature and the temperature to be determined.
By meAliurillg lhe efficiency of the cngine and aPlllying Eq. (11.4 7), one can filld the 1m-
knowu temJl,erature. Problem.
X .. liUPI, F. 11 .8. Discussion of eooling by adiabatic demagnetilation. 11 .1 A gall is maintained at a constant 11 .3 When a system jg taken from state
Sofu .io .. , One of the mOl!~ importsnL techniques used to cool a substance down to pressure of 20 atm while it expands from a A to stale B along the path ACB (see
temperatures of the order of 10- 3 -K is the method kno"'n &!! odiabatic d~m{Jgndiwtion. volume of 5 X 10- 3 m3 to a volume of Fig. 11- 17), the system absorbs SOJ of
We shall give only a qual itative discussion, bringing out the physical ideas ill\'ol\"ed and 9 X IO- J m3. What amount of energy heat and docs 30 J of work. (a) Gi\en that
omitti ng in th is illstance the detailed math- must be supplied as heat to the gall: (a) to the work done is 10 J , how much heat
ematical discussion. maintain its internal energy a t a constant
The entropy of a substance incrcases with
T value? (b) to increase iUl internal energy
by the same amount as lhe external ",ork
,
temperature more or less as indicated by
curve (I) of Fig. 11- 16. If the 8ub~tance is TI ~- ----- ----- done? Express your result in calories and
A in joules.
paramagnetic and II. magnetic field is ap-
plied, it produces all ordering effect, tending m"j(nct;e 11 .2 A gas, i!litially at a pressure of 4 atm
to orient the magnetic moments of the mol- fi~ld and having a volume of 4 X 10- 2 rna, cx-
ecules nlollg the direction of the mflgnetic T, - - - - - - - - --- (' pands so that t he relation p V _ const
field. This re~ults in a lowcritll\" of the en- holds. Under such circumstances the tcm-
tropy, all indicated by curve (2) of Fig. 11 - 16, perature, and hence the internal energy,
since the netion of II. magnl'tic field brillgs of the gas remai!!thesame.Caieulate the 0'" - - - - - - - ; ;
o work done and the heat absorbed whcn t he
about a decrease in the disorder of the
molecules. I' ig. 11-1 6. .l.diabatic dcnmgnetiUlliou. volume is doubled. Figure 11-\7

488 Thtrmodynamitt
is absorbed by the 5ys~ m along pllth
A DB? (b) The system is re~urned from
slate B to state A along the curved path.
T he work done on the system is 20 J.
D~ the system absorb or liberate heat,
and hOll' much? (c) Given that U... .. 0
and Un " 40 J, determine the heat lob-
lIorbed in the procC!!!lCs A D and AB.
11.4 A ga! undergoes the cycle shown in
Fig. 11- 18. The cycle is repeated 100
t imet per millute. Determine the ]IOWer
generated. The data are as {ollow8: At A
the pressure p .. 30 atm and the volume
V .. 2 Jilel"$; at B the pressure is 10 atm
and the volume is 8 liters.
p, atm
30
" (a{3/iJP)T - -(aK/ aT),.
, , 8 V, lite ...
" temperature T , occupies a container of
Fig ure 11-1 8
11.5 Plot the lines desc ribing isocboric
transformations of an ideal gil!! fo r three
different vo lumes all on the same graph.
Repeat for isobaric t ransformationa for
three different prcssun:1;I and for isothermal
transformations for three different tem-
llerawrcs.
11.6 Show that the work done by an ideal
gas during an isothermal expansion is
11',. _ NRT III V2/ V 1 - NRT In pI /p2.
What amount of heat is absorbed during
the process? {llint: Use Eq. (1 1.I6).\
I i.7 The heat capacity C, of most sub-
stan ces (eXC(lllt at very low temperatureS)
can be satisfactorily expressed by the
empirical formula
c, _ a+ 2bT - ,T-2,
..
where (I, b, and , are constant.!! and T is the
ab30lute temperature. (a) Tn term.!! of (I, b,
and c, calculate the heat required to ra ise
the temperature of one mole of the sub-
etance at constant pressure from TI to T2.
(b) Find the average heat capacity between
temperatures TI and T2. (e) For mll-gne-
aium, the numerical values of the eo nstanU
are a _ 25.7 X 103, b _ 3.13, and c -
3.21 X 108, when C, is in J "K-I mole- I.
Calculate the heat capacity of magna ium
at JOO"K and the average hcat capacity
bel"'oon 200"K and 400"K.
I \.8 The coefficient of cubical expansion
at constant pressure is dcfincd as
13 - (l/V)(aV faT)"~
and the isothermal bulk modulus is dcfined
M initially also at the same pressure, the
Ie _ -(l/ V)(av/a pk
Prove that
11 .9 A gas composed of N molecules, at
volume V I separated from all empty con-
tainer of volume V 2 by a removable parti-
tion. When the partition is removed, the
gas occupies the whole volume VI + V2.
Show that (a) the temperature of the gas
rcmains the same and (b) the change in
cntropy is as _ kN In (I +V 2/ V. ). (c)
Verify that as is ~iti ve.
I LlO Consider two samples of difft:rml
gasca, designated a and b, both at the same
temperature T, compOlll:ld of N. and N.
molecu1ea, Te!lpectively, and occupying
adjoining containel'3 of volumes V I and
V2, separated by a removable partition .
When the partitien is removed and both
gases are mixed, we have N. molecules of
gas CI and N~ molecules of gas b both
occupying the volume V I + V 2. Show
that (a) the temperature remains the same
and (b) the change in entropy is l!.S -
+
kN.ln (l V2 / V 1)+ +
kN. In (I V dV2)
(c) Verify that as
is ~iti ve.
11.11 Consider two saml)ies of lhe aame
gas, both at t he same temperature T, com-
posed of NI and N2 molecules, respectively,
and occupying adj oining cOlltainers of vol.
umes V 1 and V 2, separated by a removable
I)artition. When the partition is removed,
we have a sample of the gas composed of
NI + N ~ molecules occupying the volume
VI + V2. Show that (a) the te mlleratUr<l
remains th e same and (b) the cha nge in
en tro py ill
(c) Show also that if the two gases were
change in entropy would be Jero. Why?
11 .12 The lIelrnholk Jru erwgV is defined
as I' _ U - TS. Show tha t
f' - -kNT lin (Z/ N) + II.
Find I' for an ideal gas. Al$o show that t he
parameter a defi ned in Eq. (10.11) is equal
to - f '/kNT.
11.1 3 Refe rring to t he system dt'scribed
in Problem 10.33, show t hat (a) t he heat
capacity of the system can be written &II
C. - c.,,, + C. ,." and (b) the entropy of
the system can be writte n asS - S,,+ Sl.',
where
SI., V.,
- T+kNlnZ,.,.
This apillies, for example, to the computa-
t ion of the heat capacity of a paramagnetic
gas placed in a magnetic field, with
S ...... - Um..JT+kNln Z m...
11.14 A system is composcd of pa rticles
whose in terllal degrees of freedom corrc-
sllOnd to stales of energy 0, t , 21 , . , m,
ProOkrru 4"
... , where n varies from zero to infinity.
Find the ent ropy and the heat ca pac ity
due to the inte rn al degreea of freedom of
the system. [/lint; Refer to Problems 10.6
and 11.13.\
11.15 A system is composed of particles
that, due to their internal degrees of froo-
dom, can exist on ly in either of t wo sta tes,
of energy - t and +.,
in addition to the
translational kinetic energy of the parti_
cles. Find the entropy and the heat capac-
ity (at constan t volume) of t he system due
to the internal degrees of freedom of the
particles, as a fu nction of t he temperature
of the system. Plot both quantities as a
function of the absolute temperature of
the system. [lfint: St.'e Problcm 11.13.\
Ap ply your result to cal culate the magnetic
entropy and the magnetic heaL capacity of
electrons in a maglletic ficld.
IU6 A system comllO!lCd of N melecules,
each hsving an angular momentum j and a
gyromagnetic rat io g, is pla.;ed in a mag-
netic fie ld ~. Show that the entropy dut'
to the magnetic field when equilibrium is
reached is \
s.. - -kNjX [(I +~) COlh (j+l)X
~
I
2j coth :zX+ In
.1. sinh U+ l )X]
si nh t.t '
where z - gl'flm/ kT. Also calculate the
heat capacity at constant volume.
11.17 The number of particlC3 in a lIystem
is N. The particles can only be in either of
t wo states with energy +
t or - I, but the
particles do not have any translational
kinetic energy. Gh'en that t he total
energy of t he system is U, show that the
absolute temperat ure is given by
Verify that the absolute temperature is
positive (negatil'e) if U is negative (posi-
t ive). This situation applies, for example,
to a set of part icles (electrons) of spin i

wh('n they arc lllaeed in a magnetic field
and only the spin-magnetic interaction
energy is considered. [flint: First show
that
In P _ Nln2 - ;(N+ V l t ) In (N + V/t)
_ ; (N - V/t)ln{N - V l t)j
then plot In P M Il function of U. Note
that V varies from - Nt to Nt.\
11.18 Oxygen mo\ceules have a spin of I,
!j() that oxygell is II. parll.tnl1gneLic gas.
Dete rmine th e spin JllI.rtition function of
oxygen plae ....J in a magnetic field m. Ob-
ta in the energy of the gas, iWl average
magnetic moment, its spin entropy, and
its heat capacity at constant volume due
to the magnetic field.
11.19 Show that the change in en tropy
of a substance heated re\'er!!ibly at con-
stant pressure (assuming that the spedfie
heM remains oonstant) i~
S2 - SI _ l'<C, In (T2I T I).
Apply your result to I kg of water heat~
from room tem perature (298K) UII to Its
normal boili ng point (373K).
11.20 When II. ~ubSIlUlee undergoes a
change of phase (fusion, \'aporizatio~,
sublimation, clc., or the reverse), heat IS
absorbed (or liberated) at constant tem-
prrature. For "'at ('" r thc heat of fugion is
1440 cal mole - I and the h('at of \'a\loriza-
lion is 9i20 cal mole - I. Calculate the
change in entropy of one 1Il0ie of water,
given that iL is heated rcv('rsihly from
_ 200C to U,OC at a cOMtant pressu re of
I atm. The hellt eallllCit)' of ice i ~ 9.0 cal
OK- I molc- I and the h(' u l"IIlIncit}' of
8tl'ILm at con ~tant I)rc-ssure ill 8.6 elll OK- I
ntole- I .
11.21 If ~ ill II. fUllction of the "nriables x
Illid y, then
ThI'll recognize thftt from Eq. ( I 1.3i) we
-
have that
T _ (iJUl iJS)v
and
Write th c corresponding exprcSllions de-
+ Also verify that AS is posithe. !lfirll: "'or
rived by d ilTcrentinting: (II) II - V
(b) /0' _ V - TS (ealled the J1dmAollz
fru energy), and (e) G - U+ pV - TS
pV ,
(elllled the GibbJ fru elWgy).
11.22 If dE .. X d..t + }' dy is an exact
dilIerential so that X - (iJuax) ~ and
}' _ (iJ u ay)., we have tha t (aX /iJy)~ -
(a y l iJx) . Gh'cII the thermodynllmie fune-
tions (a) U, (b) If - U+ pV, (e) /0' ..
V _ TS, and (d) G - V+ pV - TS,
determine Ihe relations, of lhe type stated ,
thaL are dcrived from them; these are
called the .IJaxwell rdalWnll. [llinl; See
the Jlre<:eding problem.\
11 .23 Some thermodynamical quantities
are proll,ortional to the number of particles
(or to the mass of the system) and o~hers
are ;ndepeudent of the number of particles.
The first type of quantities arc called a l en-
.i" and the second type are called im~mt.
Dete rmin e which of the follow ing quant i-
ties are extensive and which are inte nsive:
U, lV, Q, p, Y, T, S, n, (al/ l ap)s ,
(all/aS)" C" C., }o' .. V - TS, Ilnd
G _ V + pY - TS.
11.24 Show that C, - c. - fJ2TV I t"(.
[/linl: First cXllrcss dS in terllls of dT and
dV. Theil show thaL
(aUl aV )T + p .. T(ap l aT)v.
For the definit ion of fJ and 1(, !ICC Prob-
lem 11 .81
11.25 Given Ihat p is the pressure at
which II substance ('"x illts in twO phascs in
equilibrium at tclllpenltllre T , 1l1ld V I Ilnd
Y 2 arc the volumes of 1 mole of the BUb-
IItance in each ph9.SC', show that
where I. is the mohr heat of chftnge of
phase j i.e., the hcat absorbed "'hen I mole
p&.iI!!CS from one Ilha..<re to the other. ThiJ!
expression is called ClaptyrOrl', tqllolm.
[/fi1ll; U!JC the reilltion
(JSl av' )T _ (Jpl aT).- ,
derh'cd in Problem 11.22.]
11 .26 One mole of an ideal gas at 2SC
and 1 atm is hea ted a t constant pressure
until its volume i~ tripled.
(a) l!. V , (b) 11", (c) Q, (d ) l!. S, (e) l!.Il, (f) l!.f',
(g) l!.G. (Sec Problem 11 .21 for the ddini-
tions of f' and G.)
11 .27 Compute the eha"ge in entropy,
enthmlpy, and internal energy of 1 mole of
water when it mel ts at a telllperatUf(1 of
OC and a pressure of I atm. The density
of icc is 0.9 X 103 kg 1ll- 3 and that of
water is 1.0 X IQ3 kg m -~. The heat of
fWlion of water is 1440 cal mole-I.
11.28 (a) One kilogram of water at OC i~
brought illto contact wilh a large body at
100C. When the water has reached lOO~C,
what has been the change in entropy of
the waler? or the body? Of the univeMIC?
(bl If the water had been healed from OC
to lOOC by first bringing it ill contact
with ft large body at W C and th en with
11 large body at 100C, whllt wOlild have
been the change in entropy of the water
and of t he univer!IC? (e) Explain how the
wa te r might be healed from OC 10 100C
with no change in the ('l1 tro!,y of t he
uni vel"Sl.!.
11.29 A body of hellt capacity C,] and
containing SI moles at telllJleraturo TI is
placed in thermal contact with another
body or heat capacity C,.2 and containing
l'< 2 mo les at templ'ralUro T2 . The only
process thftt can occur is 11 heat exchange.
Is th e process reversible or irre\"C rsib lc?
(a) Show that when th ermal equilibrium
i~ reac hed the com mOrl tem])Cra ture is
T _ l'<IC,IT I + N,,zT 2
:-OIC,1 + XzC,.2
I'roblt ms 491
Verify thllt T i~ a tcmpernture that falls
between TI llnd T2. (b) Sho"' that the
total change in cntroll), is
the last que~tion, ass ume that T I is gmaller
than T2 so that thl' three tempNatUre5 are
in the OrUer TI < T < T2. Then add and
subtract from t.he abovc expression for.uS
Calculate
the quantity ;.I2C,2 1n (T I TJ ).)
11.30 Assu me Ihat I()() g of water at !lOC
is poured into a O.3-kg aluminum contaillcr
initially at room temperature (25C).
Ca1culatC'" the change in entropy of thc
aluminum , of the Willer, alld of the entire
system after thermal equilibrium has been
reached. Is the llTOC(,"M rever!!ihle or
irreversible!
11.31 A liquid at a tellllX'ralurc TJ ig
miX1!(1 with an equal alllount of the 8lI.me
liquid at a teml)CratufC 7'2. T he system
is thermally ill~ u1ated. Show that the en-
lropy change of the universe i ~
and prOI"O that this is neecssftrily posithe.
11.32 Compute Jr, Q, .u V, .uff, and .uS
when I mole of stea.m at 100C is oon
densed by isothennal rompression Ilt a
pressu re of I ftlm. The heal of vaporiza-
tion of water is 9720 cal mole-I and the
density or steam in such conditions is
1.686 kg m- 3.
11.33 One liter of all ideal ga.s at 300 KG
and at II. Jlressure of IS aIm expands
isothermally until ill! \'olume is 10 liter!!.
COIll])ute Jr, Q, 6 1, all, alld 6S.
J 1.34 One mole of nitrobenzene
is vaporized at 210C and a pressuI"C of
. 1 atm. The heat of va[X1rization is 9i30
.....
 492 Tht rmodynomia 12
cal mole-I. Compute (a) Q, (b) IV, (c) tJ.1f,
Cd) .tJ.U, (e) tJ.S , (f) tJ.F, and (g) .tJ.G.
dE _ (dE/dT ) dT; then apply the prope r-
t ies of an exact differential, l1.li used in THERMAL PROPERTIES
Problem 11.21.)
11.35 The energy density E of blackbody
radiation is a function of the temperature
alone (re member Eq. 1.8). Also the pres-
11.36 Show that, for II. reversible eycle in
which only expansion work is done,
OF GASES
sure exerted by iso tropic radiation on a
IlC rfedly am.orbing surface is ",P.'.
means of Eq. ( 11.37), show that E is lIfO-
portional to T4, which is the Stefall-
By
f d: -o.
Boltzmann 111.11 (Example 1.4). [lIirn: Note the similarity of this equation to
Write U _ EV in Eq. (1 1.37) and nOle that Eq. ( 11.44).

12. 1 Introduction
12.2 The EquaJ.iort oj SlaLe oj an Ideal Gas
12.3 EquaLion oj Stale Jor Real Gases
12.4 Heat Capacity oj an Ideal Monatom ic Gas
12.5 Heal, Capacities oj an Ideal Poiyalomic Gas
12.6 The Principle oj Equiparliliorl of Energy
 p
Thtrrrwi propalitf 0/ gaftf (12.2
12.1 IntNHiuf!tlon
In the I.wo preceding cllnl)lers we have laid the groundwork for a discussion of
the general properties of !Huttcr in bulk: t he meehanieal, electrical, thermal, and
chemical properties of matter or large aggregates of aloms or molecules. We can
aPI)roach the discussion of these properties from two opposite directions. The
ezperime/!laI apwooch calls for extensive laboratory measurement and tabulation
of properties such M density, specific heat, thermal and electrical conductivities,
viscosity, elastic moduli, surface tension, thermal expansion, chemical reactio n
mtes, ctc., and the empirical dependcncc of thcse quantities on external factors
sueh as pressure and temperature, applied elcctric and magnetic ficlds, etc. This
hn.s been the traditional proccdure for those interested primnrily in a knowledge
of these properties for s pecific applications. The nhernative approach is lheortliro1.;
this ap proach consists in an evaluation of the bulk properties of mutter in te rms
of thc :l.tomic and moleculnr structure and in temlS of the intcraetions between
atoms and moleeules. Although these interactions are essentially electromagnetic,
!lOme sim plifying nss um l)tiolls of a largcly phenomenological nature aTe made
(such ns n rensonable intcrmolecular potential energy) . Becnuse of the large num-
ber of particles involved, the theoretical npproach requires 1hc usc of st.atisticnl
methods.
In this chapter \\c shat! illustrate the thcoreticall>rocedure by working out some
represcntative problems related to the thcnnal properties of gases. The extension
of the methods of this chapler to other states of matter or to special topics belongs
to engineering, physical chemistry, and applied physics, and will not be discussed
in this text.
12.2 The Equfll;on 01 Stat.e 01 un Ideul GU6
The simplest of all systems of particles is an ideal gas, and in this section we shall
obtain its equation of stale. In Example 11.6 we derived Eq. (1 1.39), thaI. is,
(12.1)
This equatio n relates the change in the partition function to t he work done by a
system and its change in temperature. For thc case of a gas, in which the only
work is e}[pansion wo rk , we have d lV = 11 dV. Al!lO d(ln Z) "'" clZlZ. Thus we
may rewrite Eq. (12. 1) in the form
kN d(ln Z) = P ;v + U7?~7' .
If thc temperature is constant, dT = 0, and !IOlving for p, we hnve
(12.2)
12.2) The tquolum 0/ $Iede 0/ 011 idtol gm 495
where the subscript 'I' indicates lhat the temperature is constant. Equation (12.2)
relates the pressure of a system to itll temperature 7', its volume V, and the internal
structure of the system, as expressed by Z. Therefore it provides n relation of thc
form f(p, V, T) = o. Hence we may call Eq. (12.2) the equation of slate of lhe
sy81em.
For a n idcal gas, the partition functioll is given by Eq. ( 10.4.0),
, V (2rmkT)3/2
Z = h3 (12.3)
which, when substituted in Eq. (12.2), gives
kNT
P=--y- (12.4)
Equation (12.4) is the equatioll of $/ale of an ideal (JCI8. It is !IOmetimes written as
pV = kN T , ( 12.5)
or, since Jl = kN A = kN I N, where N = N I N 10 is the number of moles of the
gas and N 10 is Avogadro's number,
pI' = NRT. ( 12.6)
We can de rive this equation in othcr, perhaps more direct, wnys. In 0110 case, we
call compute t he pressure of the gas by analY1.ing the change in momentum of
the gas molecules when they hit the walls of the container. I n another mcthod, we
can use the virial theorem to show that Eq. (12.5) gives the pressure of a gas when
the intermolecular fo rces are neglected. - Thc fact that we arrive at the same
result in all derivations shows thc consistency of our methods.
NO I.e 0 .. til e mea surem ent of lempera tu re. In Section 10.4 we s.ssodated the temper-
s.turc of a system of particles with the s.\'crage energy of II. ps.rticle. In Eq. (10.4 1),
which is E~ .vo - ~kT, we were more specific s.bout thc relation betwecn the temperature
of 11.11 ides.l gll.S s.nd the s.verage kinetic energy of the gllJl molecules. Howcver, we must
now considcr two import!l.lIt !l.8pecU!: J<'irst, in the defining equation (10.23), we intro-
duced two new quantities, T (the a~lute tempers.lure) and k (Bolt~mann'l constant),
and we must decide how they can be measured independently. Second, all human beings
have an intuith'e concept of tempcrs.lurc b!l.8cd on lICnsorial experience, lI.S relk'Cted by
our feelings of hot and cold. We arc all accustomed to mes.suring temperature in terlllll
of a number given by a device cs.lIed a thermometer. Therefore we must correlate our
statistical definition of temperature with this intuitivc notion.
Let us consider a ms.ss :II of a gu contnining N moleeules. If we neglect the effect of
the intcrmolecular forces, theequatioll of state is given by Eq. (12.5); that is, pi' _ tNT.
-Set-, for example, Fundamental Unirrily Phy,iI; Volumc I, Section 9.13 aud Exam-
ple 9.16.
 -
(12.2 12.3) EqUJJlion oj llauJor ,tal gau' 497

Suppose tha~ we bring the gas into t hermal equilibrium with !lOme other physical ~ystem,
which we assume may be kept at a fixed temperature. This system may be an equilib-
rium mixture of water and ice at the standard pressure of I atm. This is called the normal
freeling point of "ater. We measure the pressure and the volume of the gas at this fixed
temperature, and obtain the values Po and Yo, respectively. Ncxt we decide to assign a
convenient (b ut arbitrary) value To to the fixed tem perature, which is al!lO the tempera-
ture of the gas. Therefore we may write PoVo - kNTo. This automatically fixes the
value of the lloltzmann cOll!tant, k - poVo/ NTo, since we can obtain N if we know
the mass of each molecule.
To determine the temperature of the gaa when its pressure is p and its volume is V,
!IO that pV - kNT, we simply eliminate the factor kN, using the standard values, and
obtain
T _ To (pV/po Vo),
is independent of the substance used in the engine, and is given by Eq. (11.47), E -
(TJ - T,) / T I Given that T, is our standard temperature To and TJ is the tempera-
ture T to be measured, we have
T - To
E - - -T- -
Hence if we measure E, we obtain T. It has been found eXIK!rimentally that for a thcrmal
engine operating between the normal boiling and freezing point.s of water, E - 100/373.
If we choose T - To _ 100 degrees for those two temperatures, we again have that
To _ 273"K. The temperature obtained using a reversible engine is called the thtrmo-
dynam ic lempD"alure. This method was proposed by Kelvin. Both Kelvin and Joule
made careful e:r.:periments comparing t he temperature measured by a constant-volume
hydrogen thermometer with the thermodynamic lemperature.

wh ich gives T in terms of our standard reference temperature To and other measurable 12.3 F.,quat loll of Stat#! for R e al Gase ..
quantities. In th is way our mass of gas has br!eome a gfU thc-momder. If the volume of
the gas is maintained constant and equal to Yo , we have T _ To(p/ po), resulting in a When we are dealing with real gflSeS, we must take into account the intermolecular
cOMtant-~'olljme ga8 thermomeler. We may U!IC other substances as thermometers instead fo rces and the finite dimension of the molecules. The intermolecular forces arc of
of gasca, sueh as liquids or metals whose dimensions (volume or length) change with the fai rly short range and d eercase rapidly with the distance between molecules. Therc-
temperature. Other thermometers use electric conducWTlI (such as 1)latinum wires) fore the preSBure of a real gas will be closer to the ideal gas value, Eq. (12.4), the
whose resistance varies with the temperature. Since the equation of state of these sub- la rger the volume per molecule; i.e., the larger V /N. This suggests that we express
stances is more complicated, in practice we calibrate these thermometers against a gas the pressurc of a real gas in lem18 of the series
thermometcr. In this case the t hcrmometer agroea with the gas t hermomcter only at
the calibratio n points. Since the prollCrty chosen may not vary linearly with the gas NRT N~ A N'B N4C
temperature, thcre may be slight diaerepancies at intermediate temperatures. P = ---y- + V' + V3 + """jIi" + . ( 12.7)
We may choose the value of To on the basis of !leveral points of view. For example, we
may choose another process which conceivably oceuTll at a fixed temperature, such as in negative powers of V!N. We can consid er Eq. (12.7) as 1M tquolion oj &tate oj a
water boiling at the standard pressure of I atm, whicb is callcd the normal boiling point nal gQ.8. A, B, C, ... are quantities characteristic of each gas, called the second,
of water. Then we may decide that the temperature of this second reference point is third, etc., virial roe;fficienu. They arc functions of the tempe rature, and depend
100 uni ts, or deflrte., above To, chosen as tho normal freezing point of water. Given t hat on the s trength of the intennolecular forces. By measuring p at different tempera-
PI and VI are the pressure and volume of the gas at th is new temperature, we have that t ures and volumes, we can obtain the virial coefficients A (T), B(T), ... experimen-
PIVI _ kN(To+ 100). Solving for kN from thc equation PoVo - kNTo aud substi-
tally. H owever, to find a clue to the correlation between the viria! coefficients and
tuting this vslue in the abo\'O equation, wo find that
the intermolecular forces, we must obtain certain theoretical relations. One possi-
bility is to use the virial /Morem, which is derived in mechanics texts. * This
To - lOOpoVo/(PI VI - PoVo),
theorem, when applied to a gas, beeomes
from which we (an obtain a numerical value for To in this arbitrarily chosen 8I:ale. The
value obtained for To as a result of this type of experiment (and many olher experiment.s PV=NRT + ~(I: Fo .r;J) , (12.8)
using different techniques) ill To - 273.15. Each of the unit.s ill called a dllJru Kelvin,
designated by "K. No,,s.days it is preferred to simply assign, by definition, t he value
.".,..1... ave

To - 273.15 "K to the temperature of the normal froezing point of water. The value of wherc F i} is the force on molecule i due to molecule j, ',J
is the position vector of
thc Boltzmann constant then becolls k _ 1.3805 X 10- 23 J OK-I. molecule i rclative to molecule j, and the summation extends over all pairs of
tt is important to reali!e that the techn ique we havo explained for mcasuring tempera- molecules. When we compare Eq. (12.8) wit h Eq. (12.7), we find that
ture is based on the ideal gas approximation. If we use different gases, the re~ul\.l:! ob-
tained will not be the same because the effect of the intermolecular forces, as it aPIK!aTll in
Eq. (12.7) of the next section, is different for cach gas. Usually hydrogen or helium is
used. It is most desirable to ha ve a temlK!Tlllure 8I:ale independent of the substance
~ (L "J) = N(Nt + ~: + N:~ + .. -),
."
pai..
F iJ '
avt
(12.9)

being used as a measuring medium. We can accomplish this by using a reveTllible thermal
engine OIK!rating in a Carnot cycle (see EXaml)le 11.7) . Then the efficiency of t he cngine *See, for example, Fundamental Unu'trrily Phyriu, Volumc I, Seclion 9.12.

...
 ..
498 T hermal properties of ylUf$ (/2.3 12.3) Equation of ~lateJor real glUes 499

which in principle allows us to correlate the virinl coefficients A, B, C, ... wi U) the
intermolecular forces . T he methods of statistiealmoehanies aHow:~ mo re straight-
forward calculation of the virial coeffieienL~, as we shall presently sec. However,
because the statistical mechanics of systems composed of inter:~cting particles is
slightly more complex than that of systems of noninte racting particles, we sll(l.11
have to omit some derivations.
Let us introduce the quantity Z = ZN jN l, called the gralu/1Jarlition function
of a syster~ of nonintcracling particles. Then , noting that
InZ = In (ZNjNl) = NlnZ - InN!,
w e may also write the C{luation of state (12.2) in the form
and use a reasonable express.ion for thc intermolecular potential energy. Onee lI"e
know E p , we may ill principle evaluate Z. By applyiug Eq. (12. 10), we CM obtain
the I)ressure p and expand the result in inverse powers of the volume V. In this
way we can establish a relation between the intermolecular potential E p " and the
virial coefficients t!, H, ... Since we can determine the vi rial coefficients A, B, ...
expcrimenta!!y, this provides a very useful guide for investigating the form of
the intenllolecular I>otcntiai Ep;j on a sort of trial-and-error basis until we can
calculatc the correct virial coefficients. We shft!! i!!ustmte some of these tec hniques
in the remainder of this section.
Let us consider the multiple integral of B,4~)
Eq. (12. 12); that is,

p = k7' [001' (In z) 1: (12.10)

I = If -j e-
E

1kT
dV l dJ1 2 dJ1,,,
Allmolooul e .

J10r an ideal gas, using Eq. (12.3), we have where the SUlllmation

_ ~ [1'(211"mkT)3/2j" . (12. 11)

Lldo.l
II"
- "1.
Jv I.'

When lI"e are considering real gases and therefore dealing with interacting mol- con tains ;NCN - I) terms, whieh is the lij--l
ccules, \\"e have to extelld the methods of statistical mechanics eXI)!ained in Chap- total number of different pairs of lllole-
ter 10 to include the intern:11 potential energy Ep = LAII "ain Epij. We cannot go cules. l\oting that Iv very 8maJ1
into thc mathematical details of this extension; it is s ufficient to indicate tha.t, in o
the case of a relll gas, the grand partition function Z has the form

Z = ~. ! [(2"'1~~T)3/2r If. .Je- e.lkT dV! dV 2 dV,,", (12.12) we have that

A!!",a]~.ule.
e- E 1kT = II e-t. i,lkT,
\\"llCre the N volume integrals correspond to one for Mch molecule. This appar-
ently formidable expression is, in fact, 1\ very simple extcnsion of the partition
function for an ideal g!lS, because for an ideal gas we must make 8 p = 0 and then
".
poi,.
Fig . 12-1.
energy.

where the symbol n means the product. of all terms appearing. Also \\"hen Ep,"j is
Intermolecular potential

e-Y../kT = I. Thus the multiple integral becomes very small, the exponcntinl factor is practically I. nut (except when the molecules
If -jdV dJ1 1 2 dV N = 1'.1'. y ... = 1'"'", (1 2.13) arc m l her close) Ep;j is ve ry small, due to the short range of the intermolecular
forces (sec Fig. 12-1). Thus, using the expansion e- z = I - x !X2 - . .. , \\"e +
AI]moloculoo
can \\"rite
since each molecule nlay be found lhrollghout the entire :\vaihblc volumc. Then
(12 .1-1)
Eq. (12.12) beCOIllOS

and the quantity /;j i!; very Sillall exccpt whcn the (,\\0 molecules nrc very close.
T herefore
in agreement with Eq. (12.1! ).
Xo\\", returning to Eq. (11.12), lI"e lllU~i, write Ihe potential energy '15 ".
J>O.i r . ".
lIai,.

p = L: E'p;j T he terms lhat have been omitted involve products of 2, 3, ... fd>i, and \\"e shall
".
" . in Ilegleet them, although, in a more detniled theory, they must be considered. With
 -
(/2.3 12.3) E:qualion of d afe 101' real gme,
5fIO Thtrmlll propulitf of gllU6

The previous result is just the first two terms in the binomial expansion of the
""
this approximation we may write the integral I as
above expression. The grand parti tion function of the real g8.S, Eq. (12.12), is now
given by the expression

z
~ -,-
Nt
[V(2rmkT)'''J
h3
" ( 1 + NP)N
2V 02. 17)
The renn having the factor I obviously gives V"" afte r integration, in agreement
with the previous result for:1.I1 ideal gas in Eq. li2.13). Succeeding terms then
up to the first order of approximation. This must be compared with Eq. (12. 11)
give the contribution of the intcmlolccular forces. The iN(N - 1) temlS of the
for a real gas. The last factor in Eq. (12. 17) is the cont ribution of the intermolecular
summation are all alike, because I'i has the same form for all pairs of molecules.
forces to the grand partition function.
Thus we may write their contribution in the fonn
(12. 15)
To obtai n the equation of state of a real gas, we now use Eq. (12. 10), From the
expression (12.17) for Z, we have

where we have chosen the pair of molecules I and 2 and the facto r VN - 2 results
from the volume integral for the remaining N - 2 molecules. III cvalu!l.ting the
Inz = Nln V +N In (1 +~:) +F(T ),
double integral, we may first choose OUf origin of coordinates at molecule I to where we have included in F(T) the remaining terms that are ei ther constant or
perfonn the integral over dV 2 (Fig. 12- 2) . Designating the distance between 1 and dcpend on the temperature and do 110t affect the derivative in Eq. (12.10). We
2 by r, we may thon write
z,
now approximate the second te rm, using In (l +
x) ..... x under the assu mption
that :t (- N,8/ 2V) is smaU compared with 1 (the quantity N,8/2V is of the order
J,f/ L2 (r)dV/dV,
,
2
of 10- 4 at STP). Thus
= II {//I2(r)411"r 2dr} dV / ~~ + F(T) .
where we have used dV 2; = 411"r2 dr for the
I, Therefore
In Z = N ln V +

volume clement, because of the sphericnl 12i~

1,/
1' t
] N N'p
symmetry of the problcm. The integral ___
--,2'--__.1./,
I / '"
[ av (In Z) r =V- 2V2

fJ = 10r- fI2(r)br , dr (12. 16) Figure 12- 2 which, substituted in Eq. (12.1O), gives

2
is independent of the position of molecule 1 (so long as it is not close to the walls p = kT [!'!. _ N 2 fJ ] = tNT _ kTN fJ
of thc coulliiner), and thcrefore V 2V2 V 2V2

II hfu(r)dV 1dV: = hfJdV, =f3!dV I =,8V. But remembering that N = NN A and n= kN A, we may write

R cpbcing ;N(N - I) by iN', which is a valid approximation whcn N is vcry

(12.18)
large, we thcn havc E<!. (12. 15) in the form ;N 2 VN - I ,8, Ilnd we may write thc
intcgrnl / as
which is the resulting equation of state of the real gas expressed in virial fo rm, to
the first order of ap proximation. We note that in Eq. (12.18) we have obtained only
two terms; this is a result of the tYI>C of the approximation which we have made
HOlI'ever, if slIcccssive terms Ilrc taken into account in the expansion of B 1k T
C- , it: .the evalu~tion of Z. When we take these terms into acco unt, the complete
the result one oblaills for I is vlTlal expansIOn results. Comparing Eq. (12. 18) with Eq. (12.7), we see that the
second virial coefficient in our approximation is
1 = VN( I + N(3)N (12. 19)
2V
r
5fJ' TMrnwl prOf}(rl~8 oj gQ.Stl (12.3
- 12.3) Equnlion 0/ ,Iale /0#' r~l gau' 5fJ3

which directly relates the intermolecular interaction (identified by /3) and the
virial coefficient A(T) (delcnnincd c;'(pcrimentally). This is llJc conncction be-
twccn the intcnnolccular intcrnclion and the virial coefficients that we indicated
bera re.
We shall not pursue our diSClission !wy fu rthe r ; what we have said is enough to
ilLdicalc the method of attacking the problem of the equation of stntc of a real /12 - - 1 112 - 0
gas, and in general of any system composed of interacting tnolcculcs. The C!I8C for
liquids alld solids is more complex, and we shall not discuss it in ihis text.
o --,J------ie'"''-----------------
o '
,.; XAMI ' U ; 1%.1. Evaluate the llC(:ond virial coefficient for the ta.'lC of a gas composed '"
of nonintcl'lLcting hard sphere!! of radiu! roo ,
5olu l iotl , This ig a rather "unrealistic real gas because no in termolecular forces are
assumed until lhe center!! of the rnolceules are a distance 2ro apart, at which time a
strong repulsion !leU in. T hus the intermolecular potential energy i$ E.12 - 0 for r > 21"0 Fig. 12-3. Hard-core intermolecular 110- Fig. 12-4. Intermolecular potential
and 1.'.12 _ 00 for r < 2ro, resulting in fn _ 0 for r > 2ro and fl2 - - I for r < 2ro. tential energy. No attraction at any energy with a hard core and weakly aUrae-
This ~ha rd_eore H potential, ag it is usually called, is represcnted in Fig. 12- 3 . We have distance. live at larger distances.
called thi$ an unrealistic potential energy becausc it cannot produce condenlmtion, since
it ha~ no minimum Ilnd the!refore no stable! SCIIl!.rl!.tion between til(! molecules. However, where
it docs give us a simple! model with whic h to che.:k our phySical ideas without undue
mathenllltieal complications. Introducing the values of /12 in Eq. (1 2.16), we obl.ll.in

", , is a positive quantity, since E. 12 is negative (see Fig. 12--1) for r > 2ro. Substituting in
11 -
1, 2
(-l)br dr - -1..-(2ro)
3 32rro
- - -a- . Eq. (12. 19), using out previous definition of b and setting a _ !N!a, 1\'e obtain A _
RTb - a for the second vinal coefficient. The equation of state, to the fi~t order of
When We! su~litute this value in Eq. (12.1 9), the !lC(:ond ,-irial coefficient becomes approximation, is then, using F..q. (12.7),

A - RTN" (T'''''') - RTh, (12.20)

whe re b _ N,,(lG1rrV3) is four times the volume of the molecules in one mole. Helice T his equation is satisfied with faidy good accuracy by many real gascs, especially for
th e equation of stale of s gag composed of hard spheres, to the first-order Ilpproximation, large values of V ! N. The cocfficienu II and b are called l'all der Wall I. conslllnt T hey
;, aT(! given in Table 12-J for several real gases.

TA BLE 12- 1 Va n der Waals Con sta n ~

1:,1011.\1/' 1. 1:: 12.2. Extend the results of the previoWl example to the ease in which the
intermolecula. forces are attractive but very weak, except for' < 2ro, "'here a very
Su~tance "
N m4 kg- 2 mo\e-2
uro ng repulsion !leU in, making the molecules almost like im penetrable hard spheres.
Helium 3.446 X Ifri 0.02370
!W1,,' io'" As a logical extension of the calculation performed ill the previous e%ample, Hydrogen 24.68 0.0266 1
we may introduce rather weak but attractive intermolecular force~ for r > 2ro, as illus- Neon 21.28 0.0 1709
trated ill Fig. 12--4. T heil lI'e may COlltinue with the assumptioll that fij - - 1 for Nitrogen 140.4 0.03913
r < 2ro. But from Eq. (12. 14), if ":~iJlk7' is small compared wit.h unity, we may write Oxygen 137.4 0.03183
fl2 - - E,12/kT for r > 2ro. Therefore EIj. (12.16) gives Ammonia 421.2 0.03707
Carbon dio):idc 362.8 0.04267

1" ' ! ,- ,
2 2 32rro a Sulfur dioxide 678.1 0.05636
11 - (- 1)4rr dr + (- E,12!kT)4rr dr - - --+ kT ,
a Water 551.9 0.03049
e 2'0
 pi
I
Thumal pro~rl ~s of gllUf (I~.4 12.4) Hml aJpacii;y of an idtal monalomic gar 505

12. ~1 IIeat Capadlll 01 an Ideal JUonalom;c fin,. Another relation among the heat capacities of an ideal monatomic gas is
In Section 11.7 we defined the hca~ capacities of a substance at COllstant volume
and at. constant pressure as
"J' = G"IC v =!= 1.667. (12.25)

This relat.ion is followed rather closely by most monatomic gases, as shown in

c,. ~ ! ('U)
aTN I'
, (12.2 1) 1'ablc 12-3 (at the Clld of this chapter).

where II = U + 1J1' is the cntht\lpy of t.he substance. In addition to thei r im- EXAMI'I.E 12.3. The equation of state of an ideal gas in terms of pre83ure, volume,
portance as coefficients in several practical calculations, the theoretical calculation and entropy.
of the heat. capacities of a substance affords a means of verifying the correctness
Soh.lion, Since entropy is a property of the state of a gas, it can be U!Cd as a variable
of the model chosen to describe the substance. I n this section we shall calculate to define the state of a gas in the aame "'ay as pressure, volume, or temperature. From
the heat capacities of an ideal gas, and by comparing these wilh the observed the equat ion of state, pV .. NRT, we have
values for real g~, we shall be able to couclude to what extcnt the idea\+gas
model is a good app roxima.tion. In p + In V .. In NR + In T.
Let us first consider an ideal monatomic gas. The internal energy of such a
gn.s is purely tmnslationnl kinetic energy, nlld is givcn by U = tsR T . Using Differentiation yield!!
Eq. (12.21), we oblnin
(12.26)
Gil = !ll = 12.4715 J mole- 1 0 1\:-1
= 2.9807 cal mole- 1 C- I ( 12.22)
For t he case of an ideal gas, in which the internal energy depends solely on the tem-
perature, we have that dU .. NCy dT . T herefore tbe fiNJt law of thermodynamics,
Taking into account Eq. (12.6) (p V = sRT), we have that the enthalpy of an
&!. (11 .37), dU .. T dS - p dV, gives
ideal gas is
H = U+1I 1' = isRT. NCydT .. TdS- pdV,

Thus Eq. (12.21) gives from which (dividing by T and using t he equat ion of state) we obtain

C" = ~R = 20.7858 J mole- I 0J{-I dT dV

NC,, - .. dB - NR - (12.27)
(12.23) T V
= " .9678 cal mole- 1 C- I
Eliminating dT/ T bctween Eqs. (12.26) a.nd (12.27) a.nd using the relation C, - Cy .. R,
Therefore all ideal monatomic gases have the same heat eal)aeities, independent we have
of the structure of the atoms. We may note, from the above results, that

G,.-Gv= H, ( 12.24)

so that C,. is larger thanC I , by the amount R. The reason for this is that Cv is where 'Y .. C.lC". Integrating, "'e obtain
related only to the change in intenlal energy, while C,. includcs, in addition, the
expansion work of the gas when its temperature increases I degree at constant Inp + "J'lnV _ SC+1n(COnBt)
N ,
pre$llure. It is simple to verify that this work is exactly equal to R. When the
prc&!ure of the gas is constant, p d l' = NR dT, nnd if the incrcase of tempemlurc p V" .. (eonst)e"mcv, (12.28)
is one degree, the work daM is
which i~ the equation of state of an ideal gas ill terms of p , V, and S . If a transforma-
W ,,=
f pdV = JT r'" NRdT=NR . tion is adiabatic and reversible (i.e., if it is isentropic), the eq uation reduces to

pV" .. con!!t. (12.29)

Hence the work per mole done by the gas is R. From this proof we sec that
Eq. (12.24) is valid for all ideal gases, either monatomic or othem' isc. This equation finds many uses in processes involving gases.
 - 12.5) l1~at capacilie$ (If on ili~af poiyalomic 90! 501
Thermol pro~rliu of 9(1U8 (12.5

12. 5 lIf'lIl t -apllclllf'lI 01 an 'dc," 'olyatomlc GaM

,,
Whell the ideal gas is noLmonatomic, we must. take the structure of the molecules ,,
into accoullt when we calculnte the heat. capacities. The energy of a polyatomic ,,
molecule is composed of three ternlS: translatiOllnl energy, rotational energy, and ,,
vibrational energy; that is, ,

,
,,
,,
rle,..t

( 12.30) ,
,
We shall ignore the electronic energy of the molecules because it. seldom pllrtici.
pates in the thermal excitation of the gas. Electronic excitation requires an energy
of the order of 1 eV aL least; such energy is about. -10 times greater than the average
thermal kinetic energy at room temperature (29SI{), and therefore a temperatur<J
of the order of 10 40 ], is required to produce a substantial llulllbcr of molecules in
excited electronic states (see Example lOA). At. these temperatures, of course,
o , 3 , , 7

most of the gUJj molecules ure dissociated by C()llisions. ,,

On the other hand , the rotational kinctic energy of polyatomic molecules is of ,,
,,
the order 10- 4 eV, and therefore moleculcs can easily be earried to excited rota-
tional!evc\s, even!tt temperatures that are low compared with room teml)Crature.
,, T/e,~'J

,
Vibnltional energies are in the range of 10- 3 eV to 10- 1 eV, and therefore at. room
temperature molecules may be found in a few 10\\lying excited vibrational stutcs.
T o eOIl1 I)ute thc contribution of the intcrnal motions to the heat capacity of n
polyatomic g:l.S. we must first (using st:lIistieal methods) find thc distribution of
the gas molecules !\mollg the rotational !\l\d vibrational states. Let u.s limit. our o
selvcs to the simplest casc of a diatomic gas. The rotational kinetic energy of
diatomic molecules, according to Eq. (:),]2), is

o
where I i:; the moment of incrti n of the molecule relative to a perpendicular axis
passing through the center of mass and I determines the angular momentum of "' ig. 12- ;). Ch:cupation of rotational le" eI8 in a diatomic gas for th ree "slues of T1 9 ..
the molecule relative to the center of mass. As explained in Section 5.7, the angu-
lar momentum may have 21 +
1 different. orientations, all with the same enc.rgy, see tlmt even for hydrogen these values are very SlIlall compared with room tem
so that. the g. faclor used in Eq. (10.23) is 2l +
I. The equilibrium distribution of perature. T he v:'llues of /1'01 are illustrated in Fig. 12-5 for three values of Ti e,.
the molecules among the availnble rotational states, when we usc :\ Iaxwell-Boltz /\ g T increases, the numbe r of molecules in cxcited rOlfltiorml slates also incre:'lScs.
mann stnt istiCll, is thcn The rotational partition function Z,o', according to the general definitioH in
E(I. ( 10.:?2), is
_ .!:!..... (21 + I) _~ ' I (I+IlI 21kT - !!....... (2l + I ) _hl+1)9.IT
Z'OI = L, (2l + l )e- ' (I+1)9,!T.
11'0' - Z'o' C - Z'o\ (J , (12.32)
(12.31)
Ollce we compute the rotational pnrtilioll fUlietion Z.o" we can obtain the rota
where S, = h2 / 2/k is called the characluislic temperature oj rotatioll. Values of tional cnergy '.ot of the g:l:; by using Eq. ( 10.21):
S, are givcn in Table 12-2 for a few diatomic gases. Looking at this table, wc can
(12.33)
.We ~ha!l assume, for simplicity, that the three energies are addithe. However, strictly
speaking, there aTe &Ome eroM terln'lllmong the rotational and vibratiollal cnergie~.
...
 (12.5 12.!i) /ltal ropaciliu oj a,\ idrol polyalomic gas 509
5IJ8
TABLE 12- 2 CharacteriJIlic Temperatures for Ro- Thus In Zoo. = In T - In e. and Eq. (12.33) gives
tation and Vib ration of Diatomic
Molecules Uoo~ = kNT = rsRT, (12.35)

Substance 9., OK e., OK since kN = N R. Then the total energy at l' e. is

Hydrogen 85.5
'3120
14" u= U" + Urn' = ~-NR7' + rsRT = is /iT. (12.36)
Carbon monoxide 2.71
2.09 2260 Substituting Eq. (12.36) in Eq. (12.21), we get
O:tygen
Chlorine 0.347 81.
Bromine O.1l7 41. Cy = iH. (12.37)
0.224 230
Sodium
140 T hus, at temperatures high compared with e., thc rotfltional kinctic energy of a
l'ot./l.88ium 0.081
diatomic molecule contributes an amount R to the heat capacity at constant
volume of Ihe ideal diatomic gfl8. The SM1C result holdli truc for gflilCS composed
The total internal energy of the gas is of linear polyatomic molecules.
Now let us compute the vibrational energy of the ideal diatomic gas. We as-
U = VIr + Ural = tsRT + Urol (12.34) sume that the vibrations are Sim l)le harmonic; then the vibrational energy levels,
according to Eq. (S. 16), arc given by BVlb = (~ + Therefore, when we;)"w.
since VIr = ,sRT. To obtain the heat capacity at constant volume, Cv. we n~xt again use l\ faxwell-Boltzn13.nn sllltistics and (j, _
I , which corresponds to this
substitute Eq. (12.34) in Eq. (12.2 1). The heat capacity ill:re9.Se~ gradually With CMe, the occupation of the vibrational levels j~
the temperature, 88 indicated in Fig. 12- 6, because energy IS r:qUlred not ~nl y to
increase the translational energy of the molecules, but also to Increase ~helr rota- ( 12.38)
tional energy by bringing more molecules to excited r otational levels. Figure 12-6
indicates that, at a temperature high relative to 9" C y levels off at about iR.
where 8. = "wit is clllled the characteristic tllm~raturll for lJibralion. Its value
c, for n few dintomie molecules is given in Table 12- 2. Note lha~ in all eases 8. is
much Inrger than 8.. Also in most cases e.
is grenter than room temperature.
Figure 12-7 shows the values of l"I ..ib for three values of T18 .. As l' increases,
the \lumber of molecules in excited vibrational levels also increases; but because
8. > 8" the excited low vibrational levels begin to be appreciably populated at
temperatures at which many rotational levels are already occupied. In some
Fig. 12-(i. Variation of heat capacity at cases the molecules dissociate at energies lower than those at which the higher
oolll!tant volume of a diatomic gas due to TnnslBtion
plus rotation vibrational levels contribute appreciably to the internal energy.
excitation of rotational levels.
IRf----'-r' --------------- The vibrational partition function Zvib is
. _
Z v,b ~ -( . +I/J)O./ T _ _O. / 2T (~ _OO./T) (12.39)
- L.J e - II L.J II
oL-_________________ r
Using the cxpression for the sum of an infinite decreasing geometric I)rogression,
We can explain t his as follows: At temperatures much higher than a,. (so that
a./T is very small), a very largc number of rotational states are ?CCUPled. Also ~x" = I +x+ x2 +X3 + ... = _ 1
_, for x < I,
L.J I -x
the spacing of the rotatiollsllevels becomcs very small comp~red. WIth the th~rmal
energy, and we may compute Z.o~ by replacing the s~mmatIOII m Eq. (l2.3.) by and noting that in our case x = ,-O,IT, we have for the vibrational partition
+
an integration. We also substitute 21 for 21 1 and 1 for l(l + I}. Then function
Zvib = (12.40)

L
 ..
51. Thumal proptrlit, of (l(JUl (12.5 12.5) lItol capoeiliu of an. idtlll polyalomic ga.r 51'1

According to Eq. (10.24), the vibrational energy of the gas is obtained by

,, , d e + eO,lT
kNe .
,, U.. ib = tNT dT (In Zvib) = ;kN (12.4 1)
,,
,, Tle.-o5
Recalling, from Section 5.8, that ike. = lhw is the :l:crcrpoint vibrational energy
,, of a molecule, we recognize that the term tkN9. is the total zero-point vibrational
j ,, energy of the gas. This constant energy, although it runy be rather large, docs not
,, affect any process in which only energy differences arc involved. To compute t he
,, heat capacity at constant volume, we must add Uvlb to U t < Urn" and again +
,, apply Eq. (12.2 1). For large temperatures the quantity a.I T is very small;
,, hence, using the approximation e~ = I x + + ...
for small x, we may write
,,
,, , /'.IT _ 1= (1 + ~. + .. -) _ 1= ~. +"', (12.42)

0
'-- 2 3 , , 7 ~o that Eq. ( 12.41) becomes

,, U"ib = !kN9. + kN 7' = kNT(J + 6 ./2'f). (12.43)

,, T hus the molecular vibrations contribute to the internal energy by an amoUllt
,
,, whose value, for temperatures much larger tha n is a.,
,, T/ e..- l
~ , ,, Uvib = kNT = NRT. (12.44)

'fhis energy happens to be the Mnle as for the rotational energy given by
Eq. (12.35) . The asymptotic value of the total energy at very high temperatures is

o 2
~~---
,----- . , , 7
corresponding to a total heat capacity

Cy = iR. (12.45)

Comparing this value with Eq. (12.37), we conclude that at high temperatures the
vibrations of diatomic molecules oontribute an amount R to the specific heat at
constant volume of the diatomic gas.
Figure 12-8 shows, for a diatomic gas,

O~----~-----!2------{3------.~----",~-C-O-==-c-~,~~..t7-
---- the general t rend of Cy as the tempera- IH ------------T----?---,----
ture increases. This trend is well con- R TrRnslation,
F ig. 12-7. Occupation of vibrational1eveLs in II. diatomic gas for t.hree values of Ti e . firmed by experimenta.l measurements.
IH ---r ---- rotation, and
T T-'.../ vibration

H
From this result we have T rRnailltion
plus rotation
In Zvlb = - e./2T - In (1 - e-e.IT)
Fig. 12--8. Variation of hcat capacity at
nnd constant volume of a diatomic gIL'! due to Tnlrui1lltioll
d (I
dT n
Z)
ylb =
e. + e./T '
2T2 eO,l T _ 1
excitation of rotational and vibrational only
OL-________________ T
levels.

T~rmal properlies of gases (12.6 12.6) The pritlcipie of equipartili07l of energy 5'13
512

111. 6 The I'rinciple of E'I,liparlilion of ErJf!rgy
The average kinetic cnergy of the molecules of an idcal g:l..'l due to their transla-
tional motion is
E.v~ = 'kT .
NoW translational motion is associated with the three coordinates x, y, z required
to fix the center of mass of the molecule. We may then assume that, in view of the
symmetry of space, the average kinetic energy for the motion along each of lhe
coordinate axes is
Therefore, if a g:l..'l were constrained so that its molecules could move only in a
piane with two degrees of freedom or coordinates, \\"e would expect that the aver-
age kinetic energy of the molecules would be twice E, or kT.
Similarly, the vibrational motion of a. diatomic molecule has only one degree of
freedom, and the average vi brational encrgy of such a molecule should be E = ;kTi
however, in vibrational motion we have both kinetic and poten!.ial energy and their
average values are equal. T herefore the average vibrational ellergy of a molecule
is twice the kinetic energy per degree of freedom, or
(12.46)
B."e(vib) = 2E = kT,
and the total energy of vibration of the diatomic gas would be
U vib = NE.ve(vib) = kN7' = NRT.
(12.47) T his agaill coincides with the result given ill Eq. (12.44), which is valid fo r tem-
peratures high compared with a.
We may then establish a ve ry important rule, called the principle of equipartitiol~
of energy:
At temperatures sufficiently high so that kT is large compared with the
s-pacing of the energy levels associated with a certain (kgree of freedom
of Ihe molecules, the average molecular energy per (kgree of freedom is
!kT. (Vibrational energy contributes an amount of energy kT per
vibrational degree of freedom because of the polential energy involl!ed.)

T his principle will help us to extend the discussion of the preceding section to
polyntomic molecules. Consider a polyatomic molecule which has 3 degrees of
freedom for translational motion and f internal degrees of freedom for rotational
and vibrational motion (with each vibration counl.ing as two degrees) . T he avcr-
age molecular energy at high temperat\lrcs of a gas composed of such molecules
is given by
Fig. 12-9. Two angles are required to fix the
orientation of a linear molecule in space. Em = (3 + f)E = 3
- +
2-1 kT,

Now let us consider the rolation of a diatomic (or a linear) molecule. The and the total internal energy of the gas is given by
orientation of the axis of the molecule (Fig. 12-9) is delermilled by the angles a
~nd fJ it makes with any two coordinate axes, such as X and Y. Then the rotation U = NE. ,c
3+1
= -2-kN7 , = -2-NRT.
3+1
of a diatomic (and in gcneral of any linear) molecule has two degrees of freedom.
We may thus expect, by extension of Eq. (12.4 7) to the rotational motion of a The hcat capaci ty of !.he gas at constant volume tends, at high temperature, to
molecule, that tbe average kinetic energy of rotation of a molecule is the value

E . ,.e{rot) = 2E = kT,
und that the total energy of rotation of a gas composed of diatomic (or linear)
1l10lecules would be Now, according to Eq. (12.24), Cp - C v = II or Cp = Cv +
n, which is valid
for all ideal gases regardless of their molceular struclure. If we use Eq. (12.48)
U rot = NE."e(rot) = kNT = NU7'. for Cv, we obtain

"fhis agrees with t.he result given in Eq. (12.35), which is valid fo r temperatures CP = -5+f
2- R. (12.49)
high compared with a,.
 -
Th~rmal pt'Q~rliu oj ga.r~r
'" (12.6
Prohltrllf 515

the axis. T hus f = 3 and "Y = f = 1.33. Therefore the measurement of l' call
provide illlp.o rtant info rmation abo ut the internnl structure of (l. molecule. For
example, from T able 12- 3, which gi ves the value of"Y fo r several gases, we see that
H 20 is plana r and no~ linear , and that the inert gases are all monatomic (f = 0).
The CO~ molec ule is a nota.ble exception because, although it is linear, it hM
"Y = 1.30-1 , close to thc vlllue of a planar molecule. We know that CO 2 is linear
because its electric dipole momcnt is zero. The apl>.'IN!nt discrepancy is attribut-
able to the fact th nt a bending vib rational mode in CO 2 hIlS n relatively small
vibrational energy. This vibration adds LII"o degrccs of frecd om, and th us th e
ratio of h eat capaciticll for CO 2 ~hould be close to f = 1.285.

X
Fig. 12- 10. Three angles are needed 1.0 fh the orientation of a nonl inear molecule, such I. ~ The Ddinition of the J>erfcc~ Gas,~ P. Land~bcrg, tim. J. Phy" 29, 695 (1001)
as l:b O, in space. 2. ~Energy Equ ip3ftition: A Restatement, ~ W. l..awlcSil, 11m. J. Phy.iu, 32, 686 ( 1964)
3. In/rod uction to Cltemiwl Physics. J. Slater, Ne,, York: i\ leGrllw-Hill, 1964, Chapters
The ratio -y = Cp/Cv then has the value 9 and 12
4. Sta/ i&tical Ph yw;s, G. Wa nnie r. ~ew York: John Wiley, 1966, J>ar~ I
1' =>Cp = 5 + f, (12.50) 5. The !'cym/l un Lec/ure. on Physic., Volume I, R. Feynman, R. Leighton, and :>'1. Sands.
Cv 3+1 Ikading, ~! tlS8.: Addison- Weslcy, 1963, Chapter -1 1
Actu9.lIy f in these fOMl1Ulas corresponds only to those degrees of freedom fo r 6. Molteular Thermodynamic., J. FAy. lU>ading, .' Iass.: Addison- Wesley, 1965
which a very large number of excited slates nre occupied at the given temperature. 7. .'I Source Boak in Phy,i.e" W. :>'Iagie. Cambridge, :>'!~.: Harvard Univershy I'reSil,
ThuB if 7' is larger than 9. bu ~ smaller than e~, f corresponds onl y to the rota- [963, page 247 (Oernoulli)
tional degrees of freedom. But jf 7' is much large r than e.,
then f corresponds to
all the degrees of freedom. For a monatomic gas f = 0 and., = ! = 1.67, as
previously indicated in E q. (12.25) . For a diatomic gil.!! (nnd in gcncmi for any
linear molccu\() in the gaseous state), we have, at room temperature (when only
rotational motion counts), that / = 2 and.,. = t = 1.40. If the molecule is not 12. [ Using t he \'irLal eX]l.&nsion for the 12.3 T he Boyle lemperulurt of a real gas is
linear but plana r, like watc r (H 20), or three-dimcnsional, like ammonia (N H,), equation of !ltate of a gas lIS given by the temperature for which the second virial
t here are th ree rota.tional degrees of freed om because, in addition to the angles Eq. (I2.20), calculate t he work done by a coefficient is ze ro. Show that the Boyle
a and (j needed to fix the axis (Fig. 12-10), we need the angle 8 of rotation around gns when it cxpnnds i!!Othcrmally from a teillperatu re is equal to aj Rb. Compute
volumc VI \0 a volume V 2. Apl)ly t he the Boyle teillperature for some of the
resuJ~ 1.0 one mole of hydrogen at 3000 K ~ listed in Table 12- 1. jNoit; The
TAULE 12-3 i{a Lios of the Ileal Capaci tiu for Some G ases when it cxpnnd! from a volume of 3 X 10 - 2 Iloylc tt'mperature is the temperature at

Substance , Substance y
ml to a volume of 5 X 10- 2 m3. Compare
with the I'lIlue obtained u~ing the ideal-gas
which a renl gns mlly be cOll!idcred as
obeying the idcal-gas equation, up to lhe
e~llression. second order of approximation.)
Helium 1.659 Chlorine 1.353
[2.2 .\n empirical equation for describing 12.4 The coefficient or cu bical e~J)aru;ion
Neon 1.64 Hydrogen sulfide 1.32
Ilreal gas, proposed by \'an der Wna!!, is of a substnnce nt constant pressure is
Argon 1.668 Water vapor 1.324
Hydrogcn 1..110 Ammonia. 1.310 defined as
Oxygen
Nitrogen
1..10\
1.401
Carbon dioxidc
Ethylene
1.304
1.255
p _ ~('V).
V iJT ,
Carbon monoxide 1.404 Write this equation in vi rial form and com-
pare with Eq. (12.20). Find {1 for (a) an ideal gas, and (b) a real
 - 13.2) FtrmiDirat di,lribtllioli law 519
516 TMrmal proptrlir 13
13. 1 Introduction
UM STATISTICS In Chapter 10 we discussed classical statistics, which is chnractcrized by the
method of calculation of the probability of a given partition , slated in Eq. (10.8),
and by the :\'laxwell-BollZmann dist ribution law, Eq. (10.9), for the most prob3ble
or equilibrium p3rtition. When we discussed classical st3tistics, we ignored any
symmetry consideratiollS related to the distribution of the particles among the
different states associated with each energy level accessible to the p:l.rticles. How-
ever, as we Mid ill Chtlpter 4, there may be certain restrictions on the number of
different ways in which a groul) of particles may be distributed umong the avail-
able wave fu neLions nssocinled with ench energy state. Clearly these restrictiol;s,
of quantal origin, affect the probability of a givell partition. The theory in which
these symmetry considerations nre taken inlO account is called quantum stalistics.
There are two kinds of quantum statistics : One concerns particles obeying the
exclusion prin~lYe, and henec described by anlisymmdric wave functions1 This
kind is called Fermi-Dirac 8latislii8,) and the particles are called fermio!]::: The
second concerns particles 1I0t restricted by the exclusion principle, and described
by 11l!!l.metric wave funct ions. This kind is called Rose-Einstein statistics, and the
particles arc called b6Wn8. In bot.h kinds of quantum statistics it is assumed tha~
the particles are identical and indistinguishable. At high temperatures and low
densities, classical statistics and the two kinds of quantum statistics give prac-
tically the same results.
Tn this chapter we shall briefly discuss both kinds of quantum stat istics and
apply them 10 a few important physical p roblems.

1 ,".2 " 'c r",i- IJlrflC IJilftribfltifJR I. flfr:

13. 1 Introduction
13.2 Fermi-Dirac Distribution Law
13.3 The Electron Gas
13.4 A pplication of Fermi-Dirac Statistics to Electrons in Metals
13.5 Bose-E insleirt Dislribution Law
13.6 The Photon Gas
13.7 Heal Capacily of &lids
13.8 T he Ideal Cas in Quantum Stalistics
13.9 Comparison of lhe Three S tatistics
Let us re-evaluate the probability of a partition of a system of I)articles, assuming
that the particles are identical and indisl.inguiBhaUe. In addition , we assume that
the particles obey t/le exclusion principle, so that no two particles can be in thc same
dynlUnical state and the wave function of thc whole system must be antisymmetric.
j)articles satisfying all these requirements arc called fen/liQI/8 , after the Italian-
born American physicist Enrico Fermi (lOOI- I054), who first discussed these
systems. It has been found experimentally that all fundamental I)articles with
PiQ..! are f(':rmion s.
T o ooiWpule the different and distinguishable ways in which Il system of fcr-
mioml may be arranged for n given partition, we must revise our definition of the
intrinsic or state prob.'\bility !Ii . In quantum statistics, gi is given by the different
quantum states corrcsl>onding to a given energy; i.e., the degcneracy of the energy
slate. T o each quanlum stille there corrcsl>onds a I)article wave function. These
wave functions in tu rn life determined by each of the I>ossible arrangements of
quant um numbers corresponding to II given energy level. For example, for parti-
cles of s pin -t, not subject to mllgnetic forces, each particle nlay be in each energy
stale with spin up or down (III. = !), and so f!i = 2. For motion in a central
field, the energy is independent of the orientation of the orbital angular momentum,

...
 -
520 (13.2 13.2)
FtrmiDirac di,lribu/iorr. laUi 521
which introduces a degeneracy I..'<}\w.\ to 2l + I, which is the value of y for that.
shull do this in Examl>le 13.1.) The result. is that the most probable partition eor-
cnergy slate. We uscd this result. in Scction 12.5 when we discussed the roUttiollal resl>onds to the numbcrs
partition func tion of molecules. If the particles have spin, the totnl degeneracy is
+
2{2l 1). If, in nddition, scveral angular momentum st:des are compatible with n, = (Ii
the snme energy, as in a coulomb field, larger values of y, resulL Sincc the exclu- e.. +~E, +1 (I3.4)
sion prillciple forbids that two pa-rticles be in the I!.'\me energy stAle with the l!.'Ulle
til!S constilutes thc Fermi-Dirac di81ributiQII latc.
qU:l.lltum numbers, Ole flo'fJ flltoe lIle ma.rilJlulJI IlwII/H;r of parlirln (fermionfJ) lIlal call
be accollllllodalerl in an elte'flY lu'tl u:illlOut viola/illY the exclusion principle. Thereforc d' ~~~ p~rn.metcr fJ hcre plays the same role it has in the .\Iaxwell-Boltzmann
the II, values of il given partition c:lltnot exceed the y, corresponding to each energy IS TI utlOn h~\" E~[. ( 10 ..9): Therefore lI"e again define the tempemlure of the

level; that is, 'I, .$ (j,. syst.em of feTllllons III stflllsttc:!1 cquilibrium by Eq. (10.23); thJl~ is,
To fill the energy level 8, with It, particles, we notc that. we can I>lace the first. kT = l /fJ.
J).'Irticle in any of the Yi states il\'ailablci i.c., wc can assign it any of the y, sct.':l of
quantum numbers aVlIilable. T hus we Cfln place the particle in one of y, different The quantity a is still dete rmined b.'i the requiremcnt that 't"' . II V J t
wnys. The second I>article can go int.o any of the fl; - I remaining statcs. The eases a is . . . ' L.., , = J. n mos
I d a. negative (IUanllt.y. However, olle usually defines:l. (1lmntity IF having
third p..'lrticle goes into nny of thc fl. - 2 remaining states, and so on, until nil FI, tiC UllenSlon of energy, which is related to by the equation '
purticles arc placed in the encrgy level. The total number of diffcrent ways of
Ilrr::mgillg the Iti parUclc~ among thc Yi stales with energy E', is thuii t ~ = - k'J'.

Yj(g, - t)(fli - 2) (fl, - 1t, + I), Then E<I. (13.'1) becomes

which can be written in the forlll

(13.5)
g.!
(l3.1) The cnergy t has 11. " ......it' I
(gi nil! . . F . . ... ~ .IYC va ue III most. cases, and plays a very important role
III l>hyslC.'I1 apvheattOns; IL may be considered as praelical1y independcnt of tem-
So fllr we have takcn the exclusion prineiplc into {lCcount. H, in addition, the perature. We observe. E<I (135) [h'IL fo, " - 0 II
frortl '
pnrticlcs are indistinguishable, it. is 1101. possible to recognize any dilTerenee if the E = ., - a energy states up to
' ):\";,UII occupIed (~'.= y,), while nil the st.'ltes wilh E > EF are empty
. _ 'O Y
tl, ])nrticles are reshuffled among the states they are occupying in thc level of ( n, - . lhe rell30ll for thl,,; IS th!lt
encrgy Ei (this number is n,!, as we saw when we disc\lssC(1 the .\lnxwcll-Boltzm:lIln
distribution law). Thcrefore wc can obtnin the lotal number of differC1tl and dis.
tingui.~hnble arrnngemenL"I of FI, identical particle!! among the 0, statcs of cncrgy
lim e[E'-'pl IItT =
T_O
I
00
0 for E'i -
for , -
EF
tF
< 0,
> O.
B; by dividing expression (13.1) by It,l, resulting in
1;hiS ~lualion is shown in Fig. 13-1, in which the distribution funct ion lilY is
(13.2) p ottc fo~ (~ifferel]t ,temperatures. As a contrast, recall th;lt. ill l\la);\\,ell-i30itz_
'I,)!'
lI,!(g,
?
l~ft.nn. St~tls tlCS, ~t = ~, all particles should be nt. the ground energy level. In
We ('an find the total number of distinguish:lble different WayS of obtaining the Fertlll~DJrac. Sl~tlstlcs thiS accumulation at the ground level is prevented by the
partition Ith "2, Fla, ... among cnergy levels /<.'10 /<.'2, 3, ... by multiplying all exclUSion prlllClple, and the particles at. T = 0 occupy the lowest energy levels
the cXIJressions like Eq. (13.2) for each of the cncrgy ]e\'c!s availlible, thus giving Jljjg,
the plirtilion prohnbility :\5
T_O

= I[ FI,!(g,g,' fli)!'
(13.3)

Then, as we did with the :\ Iaxwell-Boltzm:utn dilStribution bw in Chnpter 10, we Fig. 13-1. Distribution function n,/ g, lIigb T
at three temperatures in Fcrrlli-Dirac
must find thc most ]Jrobable pnrtition by computing the maximum of In P. (We statistics. O;-------------~.,;--> ..:O,...-----E
.
 ..
13.3)
W The tltdr/)li 9(11 5'J3
(13.3

522 Q!iCllllum lIalidict e must eousider only the dislrib r

~~ce~I~;rrt~::IS in Ihe upper or un~I;:: ~o.~':rl:~S
g
:mon the continuous mnge
~
available up to the energy lV . Hence the cnergy fV gives :\11 indication of the
We shall I fO,re place our zero of energy at the bo ailed the conduction band.
e~e~~a~;~~I~I~~I~ ~\~~~:li!~fll~~ee~onduclion
maximull energy of the fennions in the systenl. Therefore ft' is equivalent to the

~s up~r
1 as their the electrons move freely band.
fermi energy, which we introduced in Section 6.4 when we discussed free elec--
conduction b:.l11d. This inductor, so long
t.~!~l~t~fied
trons in mctnls, and hence we shall give it the same name here. At higher tem- tion, which was full , '
\>craturcs, stales with energies greater than lV begin to be occupied, by a transfer 111 .Chnl)ter 6. Again , s ince :h: :\:;:onable 3SSump-
p~~~e:ll~l\fIlY replne~,'
the electrons in the

~ +
of particles from states of lower energy. However, essentially only those slates in Eq. (13.5), M we did con.liuliollS, we must s:;ct(rnE')1l o!
with energy dose to EF (we nffected for temperatures such that. kT lV The trons with e nergy betwccn E nnd
u" E or dBnn Ideal
is gas . '1'1 ' ) y
IUS the nllrnber dn of dee-
dE
retLSOn for this is that all low-cnergy states are fully occupied nnd the exclusion
principle prevents the nddition of further fermions to those states. Thus, as IIhown
by thil curves in fig. \3- 1, only those fem,ions with energy dose to l }' can mOve dn = gCE) dB
into higher unoccupied IItates by l~bsorbing
the relatively small energy kT. The
elt-: ,v )/I<T +I' (13.7)
temperature e.", for I\'hieh ket' = EF, is e:llled the Fermi temperature.
wh?re the cllergy E is me:\Surcd f
f~~;) (Jd(7-)g~~eS".~he number of states~llln tl~~ee!I::~~r1;,O"f "I I:,~teonduct ionband and
" may :lg'~in
EX,IMI' U:: 13. 1. Derivation of the Fermi-Dirac distribution Illw. ,
to take i t ' U!lC expreSS10n (1039) I
. eJ' g" '-'" ween F
[l1I<
I I'
~ dE ~+
501"'';0'' : 'I'IHl problem, Ill! in the case of l\l ll.xwell-Boltzmann statistics (Ex!l.mple 10.1 ),
consis~ in finding the ma;.:i!l1um of In P subject to the conditionS that E, 11, - N II.nd
. . n 0 accOunt the two >0 'bl
each glvmg rise to [l. d.iT'
. ..,)lIt we musL multi I ' .
I 581 e oneu\ntlons of the Sptn
I elent st!l.te for t he sam" '-',
. 0 f thep electrons
" ...! ergy; that is,
~
.-
It- by 2
'
E; 1I,E, _ U. joint we obtain hi P, using Stirling's approximation h) "XI - :l: In;l: - ;1:.
We thus find that gCE) dE = 8J!"VC211l3)1/~
h . /2 dB.
/~1 ( 13.8)
In P _ L: [gi In gi - 11; In n; - (g; - 11;) 1n (g; - 0;)1
3

If we substitute Eq ( 13.8) in E{ ( 13.7), we obtaiu tl Ie lI11ml>cr dl1/dE of free

Nc;.:t we compute -d(lu P) alld equate it to :rero, to obtain the maximum of P, electrons per unit energy range (1-8 I
( 13.6)
-d(ln I') _ L: {In n; - In (g; - n;)1 do; ,.. O.
dn _ 811")1(21113)1I~ e ll2
, dE - h3 ell: ' p)/tT + 1. (139)

When we combine E(I. (13.6) with Eqs. (10.15) and (to.1 7) (that is, E;dn; - 0 and This is the
E. B;dn, _ 0), which again hold in this case, multiplied, respecth'c\y, by the faetorl a in gene m,oI fl"enll1-Dlr:lC
f rcc fcnniol1s
<
rormub for the ene""U d'
It' <eJ
.
Istn b ution of frcc d t
temperature and fo, t ' IS re presented in Fig. 13- ' fo 7' cc rons, or,
I ' a ellll>cmt I' I - r - 0 f I
il.nd.8 (recall E)l:ample 10.1), we then arrive at a ready considered IIII'd b .ure I1gl com pared "ilh e _ -Ik' ora Oil
were dlsc '\ ." !stn utlon in SectIon 67 F - f t" ' We have
In n; _ In (gi - il;) + ",+.8 E; - 0 TI I~ US'i~ 19 cleetncal oondueltvit),. . 111 n quahtntive IIUY, when II
Ie ernu
~ ene ..... " us , f t '
Ulg tat E{I (13.9), intcgmted over all)en~~ll::rat~re m:l)' be obtnmed by reqmr-
. h ' eJ < IInc IOn of tI e t
" _i l j _ t _ .. -~lIj .

gi - IIi
g ,gIve the total llum"- ....:1' N 0 f elec-
1

,
I

t
Solving for 0" we fina\1y obtain r~. (13.4). "
iii<:
T_O

.;1.:1 TIll' E'f'Itron t;IIH

'fhe most cho.l'lIetcristie system of fermions is that of eleclrons in n metnl, since,
ns we Stll\' in Chapler 4, electrons ohey the exclusion principle. I n Chapter 6 we
considered the energy levels of \ he electrons in a metal and showed that they
are grouped in bandi!. The lower b!mds arc filled with electrons at prl\ctically all
system f' .
Fig . 13- 2. [, ~erg:y (l_~tribution
,. or n
Ot---------------;,.,,-~~"------E
temperatures o.lId we do not. hnve to consider them. Bllt. the U\lpcr band is only tures. o cnmons at three t"~mll('ra-
'I pnrtill.lI~'
fillcd with electrons up to l\. certain energy level. On tho.t basis we intro-
n d\lced the concept of Fermi energy in Scci.ion 6.4..
 (13.3 . 13.3) The elulron gru
524 QUflll/um lIu/irlicf 5'5
TA IU. E 13-1 Fer mi E"e rg r a nd Fe rmi Tempera - EXAMPLE 13.3. Determine the kinetic energy of the nucleons in a nucleus, assuming
ture of Se.e rol Metals that there are two systems of fcrmions (neutrons and \lrotons) at very low lcmpcralure.

Metal tv , eV e", QK 5olu'io," , We may use Eq. (13.10) to eliminate t, in the eXllression for U obtained in
the I)Tevious example by .... riting
L; 4.72 5.5 X 10"'
Na 3.12 3.7
K 2.14 2.4
C" 7.M 8.2

A,
A"
5.51
5.54 ...
6.' In the nuclear ease we have t .... o kinds of Ilarticles, neutrons and I)rotons, their numbers
being Nand Z, and the volume V i~ commOIi for both. Thus, neglecling the slight mass
difference of the two particles, the total kinetic energy is

trons in the conduction bftnd. Assuming that tr is practically independent. of T,

3 (3)~13 II~ N"'~ + Z~13
U, = 40; ;; 1" ,3 .
we may compute N III. T = O. (We did this in Section 6.4.) T he resul t is
But [reeall Eq. (7.2)1 the nuclear volume is V _ ~ .. R3 _ ~r~11. Therefore
E'
f
= .!i:..
8m ,..V
(3N)2/3. (13. to)
U, .. ~ (~) 2 13 .i:... N"13 + Z513 _ C N" ,3 + Z5 13
Thus we can obtain the Fermi energy of electrons in u metal if w~ know t he num- 40 4 .. 2 mr~ A 213 A 2/3

ber N / V of cond uction electrons per unit. volume. T able 13- 1 gIves values of EF, where
IlS well u.s of the FCr!lli tem \)Cmture, 6", for several metals. 2
3 ( 9 ) 213 h U
, - -0 - , - 2 - 3.74 X IO- J - 23.4 MeV.
4 4.. mro
EX ,IMI'LE 13.2. Determine the total energy of a group of N fermion!! a~ very low
temperature. We know that A - N + Z. On the other hand, let us call D _ N - Z . Thus
501,, ' ;0'" The total energy U i~ given by N - ;(.4+ 0 ) ,od Z _ ; (.4 _ 0 ),
eo that
u- fEdn - fE:;dl?
,od
Sincc ~he temperature is very low, we may usc (as a good apI)ro:.;imMion) the \alue of
dn/dE for T _ 0, which is jun II(E'). ThUll Substituting these values in the ex pression for U, ....e obtain
a
I( D)'"+ (I -AD)''').
112
dn _ 8.. V(2m ) E"2.
U, - 2~13C"1. 1+]"
dE 11 3
Also we jutegra. te only from 0 to tf. Thus +
Using the binominal expansion (1 :r;)~ _ 1 n:t ;n{n - l )x 2 + + and keeping + ... ,
in mind the fact thlH OJII is, ill general, small compared with unity, ....e obtain
U _ 8..1'(2111 J ) 112 /0" f...312 dE _
50 50
2

3A + 0 )12+
11 3 0
1+ ...
We may writo this expression, using Eq. (13.10), as
50 5 D2
u- iNtf,
1-"3 A+9 .4 2 _ ..

which is the minimum CIl{'rgy of a system of N fe rmions. The average cnergy per particle Thus, to t he order of approximation we have chosen,
;,

..
,,.
-
QUCln/um slatisliCl (/3.4 13.4) AppliCCIlioTl of Fumi-Dirac rlali,IiCl /0 ekc/I'QI!'

The first term g i n!lI 1111 energy proportional to the total number of p&rliclCl1, while the TAULE 13-2 Va lu es of th e Work Fu nc tion " a nd th e
'"
second gives a contribution propohionai to the differenctl II! - Z. Recalling OUT dis- Th e rmi o ni c Cons t ant .A, Obtained Ex-
cussion of Section 7.5, we recognize thll~ the fi rst term !s included in the term provor- perime nt All y from t::q. ( 13.11)
t ional to .4 in the total energy formula, Eq. (7.1 1), while the second term co rre~ l)()nd s to
().4(N - Z)2/ A , so tha~ I\Iclal t/I, cV A , A cm- 2 - K - 2

tl~ _ t(2- 213C) _ 8.33 Me\'.

T hi s value is about onc-third of the empirical msult for CIt. This disagreement is not
C.
C,
IV
...
<'8

4.'
120
48
75
surprising when we conside r t he crudeness of the model used. 1'< 6.2 32
T. 4.( S5
Ki 4.6 30
13.-'1 / Ipplication 01 "'f'rnli~IJirflC SI,,/Illt/ell C. 3.2 60
to Eleclronll in Itl,-laiN Th 3.4 60
Mo '.3 60
We shnllnQw consider some physical effects in metals, effects t.hat arc explainable
in terms of Fcnni-Dirac statistics :l.1>piicd to the free electrons in met..,ls. Fig.
me 13-3 shows (t plot of the potentinl energy of nn electron both inside a metal to escape, we can obtain the thermoelectric curre nt density j coming from the
nnd at the surflU:e. The potent.inl energy nent the surfacc is givcn by the curve metal su rfnee in terms of the temperature of thc metal. The result is
AB. At nornml temperatures the conduction band is essentially filled with dec
tronsonly up to the Fermi energy Ep, as shown by the distribution curve in part (b).
T o extract an electron from the metal it is therefore necessa ry to give the electron
at least the energy designated in Fig. 13- 3 by eI/>. This is, for example, what hap.
pens in the photoelectric effect (discussed in Section 1.4), in which photoelectrons which is called the Richard80n- Dushman equation. This equation is not obeyed
are emitted only if h" > el/>. The quantity 4> is called the work func;tion of the rigorously, for several TCfLSOns. In the first place, electronic emission is very sensi-
metal. At high temperntures, however, the occupation of electronic states extends tive to surface conditions as well as to the orientation of the surface relative to the
over energies well abovc f r . If thc temperature is high enough, somc electrons ac- crystallaUiee of the Illelal. Also, as the temperature increases, the work fUlletion
quire energies larger than E~ + e4> fi nd escape from the metal. This is the process varies because of the increase in the number of electrons having an encrgy above
cnlled IhermiOllic tmiuion, and it is fundamental to the operation of electron tubes. lhe Fenni level. T nble 13- 2 gives some experimental values of I/> and A for sev-
Using lhe FenniDirac distribu tion law to compute the !lumber of electrons eral metal!. The use of l\"laxwell-Bolt:t;mann statistics gives II. different tempera.
arriving at the surface of the metnl with enough energy and a direction of motion ture dependence, and thus themlionie emission is an indirect proof of the fact that
electrons follow Fcnni-Dirac statistics.
Another illustration of the existence of a Fermi energy in metals is the conlact
--------r-~---------
E
potential differel!ce between two metals. Suppose that we have two metals A and
Ii
B, not connected electrically (Fig. 13-4a). In the absence of any external electric
field, the potc!ntial energy of an eleetron ou~ide the metals is zero and the respec.-.

i
-_-L.._-l--.,- ' " - --7
.
,
,
l'_O

...I ..,
" +
+
-f'1--f'r-.Pr-i- -J' - - -oi:""'--- d"l dE 8 + 8
+
---_1+
(.) (b) (.) (b)

Fig. 13-3. Conduction band in a metal at room temperaturc. F ig. 13-1. Origin of the contact potential difference.
 ..
528 (13.5 13.5) 529

live Fermi levels of the metals are at energies e4>.~ and e4>/J below the l)Otcntiai a parlicuhl.r case:
energy outside t.he metals. Let us suppose ~hat <1>8 is larger than </lAo Then when
the metals nre not connected the Femli level of A lies higher than the I~en\li level -
a
I- I - 2
- I0 - I-4- - - I - I- 2 - I - ...
I -2
of B. When the two metals are connected electrically (Fig. 13-1b), the more
energetic electrons from A will flow or diffuse into H, filling the levels above the T he total number of possible arrangements of particles and divisions is equal to
originlll Fermi level of B and emptying the upper levels in the conduction band +
the numbe r of permutations of 11,+ fli - I objects in a row, whic h is (/1, I); - I) !.
of A. &\uilibrium is reached whell the upper occupied levels of the conduction But because the particles are identical and indistinguishable, all permutations that
bands in A and B are C<lualizcd. Hence metal A , which has the smaller work differ only in the ordering of the particles are the same. Hence we have to divide
function, becomes positively charged, and metal H, which has the larger work the above number by 11,!. I n addition, all pennutations of the divisions yield the
function, becomes negatively charged. This results in a potential difference be same physical state. So we must also divide by (g; - J)!. The total number_ of
twccn the two mctnls, which is esscntilll1y equnl to <PB - <P,t, in agreement with distinguishable arrangemcnts of the n, particles among the go states therefore has
the e,,]>critllcntal valuc. The ]>otential energy of an electron :lS it moves from one th r value ,I t """'\
metal to the other, act"OSll the space betwccn them, after equilibrium is atlained, -,..... (Ili+g,' - 1)1
9 , I- . .-J
is shown by the solid line in Fig. 13-4 (b). lI,!(g, I)! ....... 'V'5 -" I (13.12)

We obtain the total nut\\ber of distinguishable different ways of forming the par-
tition Ttl> 112, ?l3, .. umong the energy levels Elo E" B a, ... as we did before, by
E"perience h:U! shown that there are systems composed of ide7ltical and indistin- llluitiplying 1111 the e"pressions like Eq. (13. 12) for each of the energy levels avail-
gui8hable particles that are ,tOt restricted by the exclusion principle. In such able, reSUlting in a partition probability of
systems there is no limit to the number of these particles that can be in the same
quantum state. The wnve function deseribing such a system of p;\rticles must be p = (nl + {JI - I}!. (nl + g2 - I)!. (n3+g3 - I )! .
nl!(91 I)! 1l2!(g, 1)1 n3!(g3 J )!
symmetric. Particles satisfying these requirements are called bo801t" nfter the
Indian physicist S. N. Bose (1894- ), who first invetltiguted the statistics of
this kind of particle. It is found eXI>crimcntally that all particles with integral
= n (n,'+ g, -
; ni!(gi
I) ! .
1)1 (13.13)
spin (0 or I) are bosons. Thus helium nuclei and mcsons are examples of bosons;
4He and H, gn.ses also obey Bose-Einstein st:t.tislics. Our next step is to find the most probable partition by computing the maximum
I n Bose-Einstein s tatistics, a.s in Fermi-Dirac statistics, the g/s give the degen- of 1n P. (We shall do this in Example 13.4.) Tbe result is that the most probable
eracy of CReh energy level. To compute the different and dis tinguishable ways itl parlition corresponds to the numbers
which a system of bosons may be arranged to produce a givcn partition, we first
evaluate the number of distinguishable tlrrangements of tli particles among the (13.14)
go states corresponding to the energy level Ei which result in symmetric wave
functions. This number of arrangements is equal to the number of ways tli ide ntical this constitutes the BOIe-/:.,'inslell! dislribuliQlt lau:.
objects may be. distributed among gi boxC8, without limit to the number of objects The parameter fj plays the same role here as it did in the ~ laxwell-Boltzmann
in a particular box. To obtain this number we proceed o.s follows: SUl>poSC that and Fermi-Dirac distribution laws, and we again define the temperature of the
we place the II; particles in 1I. row and distribute them in the gi quantum states system of bosolls in thcrmal equilibrium by E q. (lO.23); that is,
available by placing g, - I divisions at appropriate places, a.s shown belo\\' for
kT = l/fJ .
That a nucleus such as 4He, composed of four fermions, must be a boson can be seen Then E(I. ( 13.14) becomes
very easily. Consider the wave function dellCribing two helium tlucld. To interchange
the two nuclei, we must interchange all the fcrm ions. Every time lI'e exchange two fer-
mions the wave function of the syst.em changes sign. But .IIincc thcre arc four pairs of (13.15)
fcrmions in the .IIystem, the exchange of all fermions leaves the wave function unchanged.
That is, the wave fundion of the system is symmetric in the t wo nucki, although i~ T he constant (r, as before, is detennined by requiring that L, 1t, = N; a does not
is antisymmctrie in each pair of fermions. This logic applies to any syst.em in which
"particles- (nuclei, molecules, etc.) are COm]106e<i of an wen number of fermions. Such have a special meaning in Bose-Einstein statistics as i~ does in Fermi-Dirac s tatis-
~particles~ thcn behave as bosons. tics. Bceause 11i cannot be a negative number, (r must be positive.
 (13.5
530
13.D) 531

13.6 Th @ I-hoton GUll

r
Perhaps the most important application of Bose-Einstein statistics is to the analy-
sis of cleetrolllsgnetie rndialion trapped in a cavity and in thcnnal equilibrium
with the atoms of the walls of the cavity. As we said in Section 1.3, this is called
1.0" T blackbody radio/ion. The atoms of the walls of the cavity arc continuously abso rb-
F ig. 13-5. Distribution function'll ;!", at
two temperatures in Bose_Ein~lein SUI.- ing and re-emitting rndiation until equilibrium is reached; this happens when the
t istics. rates of emission and absorption of radiation are the Dme. At equilibrium the
spectrum of the traPl>CCi electromagnetic r:t.dio.tion hIlS a well-defined energy dis-
tribution; that is, to each frequency there corrcsponclq an intensity of blackbody
rnd ill.tion which depends solely on the tempernture of the walls and is independent
lliglt T of t heir materiaL
I n Section 1.9 we saw that when electromagnetic rndintion inlera.ets with mat,..
ter, it behaves as if it were composed of "particles n called photons, en.eh of momen-

ol---~---=:::=-e
tum Ii/X and energy hv, where X is the wavelength and v t he frequency of the
radi ntion. We lllny then MS\Lme that t he equilibrium blackbody radiation behavcs
The distribution of boson5 follows the trend indicated in Fig. 13- 5, in which
as a lJholv1l. gas. The photons are assumed not to interact. among themselves,
only with the atoms of the \\"1111. Since photons are lLot disting uishable and nothing
the distribution function )~;/gl is I)iot.tcd for two temperatuTCs. The Bose-Einstein
prevents many photons hnving the snme energy (ex perience tells us that the in-
distribution tends to emphasize t he lower energy levels more than the :\[nxwcll
tensity of the rod iatiOIl at each frequency may be incrensed without limitation),
Bolt:j;l1lo.nn distribution does, because of the negative sign ill the denominator.
photons can be considered as hosons, obeying Bose- Einstein statistics.
One eharneteristic situation must however be laken into account in this case.
f:XA MPLt; 13.4. Derivation of the Bose-Einstein distribution Illl.
T he mWI~r of ph%lls is not constant, since they can be either absorbed or emitted
!)Qlu tioll' This problem, all in lhe IlrcviolLS two cases (Examples 10.1 Ilnd 13.1 ), C(l1l- by lhe atoms in the walls of the cavity. Therefore condition (10.15), Lidn, = 0,
~is~ in finding the maxilnum of In P subject to the conditions that ~. 'fI; - N and must be dropped; this means that the parameter a is not IIcwssa.ry. Theil we
.E,' 'fIiE; _ U. First, using Stirling'S formula, we compute In P, and ob tall\ must set a = 0 in Eq. (13. 15), so that 111 """ g.j(eE;!tT - I). In addition, the
energy spect rum of the photons may be treated Il.8 continuous if the cavity is
In P - L: 1(", + Vi - I) In (11.,+ IIi - J) large compared with the aver:t.ge wavelength of the radiation, s ince in this CMe
- J'li In ni - (gi - 1) In (gl - \. the energy difference between succCS!5ive allowed energy values or wavelengths is
extremely small (recall Fig. 2- 10).
Next we obtain the maximum of P by setting d(ln P ) equal to &ero. The r('sull is Under these conditions we must write Eq. ( 13.1 5) with o. replaced by g(E) dE,
-d(ln P) _ I: [- 111 (1'11+11;- 1) + In n,jdni - O. (13.1G) resulting in
d _ g(E)dB .
n - eE/tT _ 1 (13.17)
The nexUtepis t.ocombine Eq. (13.16) with Eqs. (10.15) and (10. 17) (thatis,.Lldn; - 0
and LI EI dn; _ 0), which expr('ss the conscrvation of the number of partLcles and of
Because the energy of the photons is related to the frequency by E = Iw, we may
energy, multiplied by Q and p, r~pectively. This results in
introduce a function g{I') such that geE) dB = g(I') d~, where 0'(1') dl' gives the
- In (nl+ 11,' - 1)+ In lIi + Q+fJE, - O. number of oseilbtory modes in the frequency range dl' corresponding 10 the energy
range dE. We previously obtained the number of oscillatory modes for waves
If we assume t hat 1'11+ Viis vcry large compared with I, we may nrglccl the I in the first trapped in It cavity of volume V in Eq. (2.20), but we must. mul tiply by 2 to
term in thc above eq uation nnd we have Rccount for the two independent directions of polarizlltion, sincc electromagnetic
waves are transverse. Therefore the number of stales in the blackbody radiation
11\ ~ -
nl+lI;
- Q - fJB; +
with frequency between v and I' dv or energy between r: and E +dE is

8"/TV
Solving for n" we obtain Eq. (13.14). geE) dE = ,
g(v) dv = - a I'
2
dIJ. (13.18)
 ..
(l3.6 13.6) Tht photon gIJ$ 533
532 Quan/um ,lalul iCl

Let us consider two levels of energiCll Eland 2, occupied by N I /U"ld N 2 atoms, rc-
Thcrdore we may write Eq. ( 13.1 7) Il.8
~peeti\'ely (Fig. 13-6). The photons corresponding to transition~ be~..... een these two
le\'els must hs\'c an energy II" - 2 - EI. Atoma at le\'e! /:.'2 may juml) spontaneously
8 -Y ,'d, (13. 19) into level E 1 Let us call A~l the oorTCSllOnding spo ntallCOU.'l cmission transit ion prob-
dn = -,., e~;"'''''-
b1tr _
ability per unit time. It radiation of frequency .. is p~scnt and it.s energy dcnsity is E(.. )
absorption transitions from EI into E2 are produced. It is natural to assume that th~
The encrgy oorrcsponding to dn photons in the frequency range dv is (hll) dn and number of such transitions per unit time is ProllOrlional to the energy density .:(..); that
the energy per unit volume is (hll) dn/V. Filially, the energy density distri bution is, the induced absorption transition probability IlCr un it time is B I 21:(.. ), ..... here BI2 is
&(11) in blackbody radiation is defined by the transition probability per un it lime and unit intensity of the radiaLion. But the
radiation, because of itl; interaction ..... ith excited atoms at level E2, also produces emission
hv dn t ra nsitions from E2 to El ..... ith an induced emission transition probability per unit time
E(V) "'" V all J
8 21(")' Therefore the total emission probability per unit t ime from level E2 to lewl
E I l.i A21 +821{")' If there are N2 atom~ in le\'el E2, the number of atoms that jump
so that. &(11) dv gives the energy per unit. volume corresponding to rodiation with per unit lime from E2 to EI is [1121 + B21t:(~)JN2. At the same t ime, the numbe r of
+
freq uency between II and II dv. By virtue of Eq. (13. 19), this energy density is atoms that jumll from EI to 2 per unit time i~ HI2E (..)N 1. T hercfore the net change
given by per unit time of atoms in level E2 is equal to the rale of gain by absorption minus the
rate of loss by emission, or
(13.20)
dN,
Tt - ~ - ~,
Emloolo~
T his is the celebra ted Plonck radiation equation, which WM stntcd without proof
in Eq. (1.8) and is re presented in Fig. 1-5 fo r different temperatures. T he agree
..... ith an equal (but opposite) gain for the lower lc\el. Wh<'11 equilibrium is established
ment of Eq. (13.20) with the experimental facts is strong support for the idea of between the a toms and the radiation, we must have dN2/dl _ 0, or
radiation as being composed of photons that. obey Bose-E instein statistics. We
remind the s~uden t that it was the problem of blackbody radiation which prompted
Pb nck to assume that when radiation interacts with matter it is absorbed or
emitted in energy quanta equal to hll. However, Planck's original derivation is 80 that the number of absorption and cmission transitions per unit time bc~ween the t\lo'O
not considered sound because, on one hand, he assumed that the atoms of tho levels ia the same. If the atoms are in therm:!.1 equilibrium and follow ) laxwell.Boltzmann
wnlls of the cavity acted as oscillators with an energy E = nhv instead of an energy statistics (which is 11 reasonable U'!umption ill most C&SCll), then
+
E = (n !)hv, and because, on the other haud, he used :>'laxwellBoIU,mann
statistics. Surprisingly, his result was correct. But if lhe zero-point energy !hv
is included in Planck's calculations, the resulting expression is no longer satisfactory. 150 that
T he problem had to wnit !!Cveral years until a satisfactory proof, as given in tho (13.2 1)
text, was found.
E(..) _ Ih d BI2
EXAMPLf: 13.5. Discussion of spontaneous and induced radiative tran~ition8. ebJlcT _ B2 d B u
5<>1'.io,, ' In Section 1.7 we CX1)lained tha~ a ~ystem in an excited energy level may fall Whcn we compare this with Eq. (13.20), which gh'ClI the energy density for radialion in
to 11 lower energy level spo ntaneously, or it may be induced (or stimulated) to jump into equilibrium with matter, we find that
the lower level with the emission of radiation, if rad iation of the proper frequency i~
prescnt.
_________"NC,C':':':'m=-________
E,

A21+B:lo:(~) 1 a result first obtained by Einstein in Hili. T he &ccond relation shows that the induced
emission and absorption probabilities per unit time arc equal. The caleulation docs not
allow us to obtain the values of A 21 , B21 , and 8 12. They must bc derived using quantum
E, mechanical considerations.
Fig. 13-(i. Induced and ~po ntaneous transitions.
 Quunlum I/o/ufie. (13.6
53' 13.6) Th~ photon ga& 535
From Eq. ( 13.21 ); with B'2 _ B2L, we obt-ain the ratio betwccn the $polltaneous In this caS!', we may write
emi!!Sion probability A21 and the induced emission probability 82I E(") when maIler is
in equilibrium with radia tion as Emission rate N2
Spontaneous emisaion probability _ ~ _ e~I.r _ J. Absorption rate = N, .
( 13.22)
Induced emission prob3bility 8 21&(")
If the substance is in thermal equili brium, N 2 is ~ m",ller than N I and t he emission rate
Therefore if h. kT , spontaneous cmillSion is much more probable than iuduccd e m~ is also smaller than the abso rption fale. But if, by !lOme mean!!, lhe relati ve population
Irion which can then be co mpletely neglected . This holds tfue in the Ca5C of e1cctromc of the excited and ground levels is inverted, !!O that N2 is larger than N I, making the
tr;n'sitions ill atoms and molecules and in the case of I1Idi!l. tive transitions in nuclei. But ratio N21NI larger than I, then t he emil\!iion rate is larger thall the ai).'J()rption rate. In
if h .. kT, Ill! it is in the microwave region of the spectrum, induced or stimulated other words, if radiation of energy d en~ity E(,,) pll.SllC~ through this system, the radiation
emi$llion may become important. tha.t comes ou t has more photons of frequency ~ than the incident radiat ion Wig. 13-7(b)],
Induood emission is the result of the action of t he inooming nu:iilltion on the a tom! (or resulting in an "amplification~ of the radiat.ion at tha t fn!<tuc ncy. This is only true, of
molec ules) of the substance. lienee the forced atom ic oscillations bear tI. constant phase cou rse, if 2 - EI ~ h ~. Since more atom~ are de-cxcited than e.~cit.cd , the upper level
difference relative to t he incoming radiat ion. Thi ~ meSons that all &toms radiate in phase, begins to be depleted, !IO t hll t t he a.mplification is decreased until thermal equilibrium is
and lherdoro indw;;~ eminion it cohtrenl. On th e other hand, spontaneous traMitions re-c~t.abl ished . Thus, to sustain 0. constant amplification, it is necessary to eontinuously
occur at random, with no correlat ion between the limes at which tl.toms undergo transi- replcnish the atoms in the upper level or to remove atoms rrom the lower le\cl by some
tions. Therefore th e phases of atomic fadiations are distributed randomly. We then say other means. The devices in which thi~ is donc are called nlilacra and Illser6. These arc
that 6ponluIICQUa emi66iQII i6 irn:ohCTlmt. coined words, acronyms for "?llicroll'a ve Amplification by Stimulated Emission of Radia.-
tion ~ and "Light Amplification by Stimullllcd EmiSll.ion of Ho.diation," depc nding on thc
";XAMI' I. E 13.6. Discussion of mase rs Ilnd lasers. rcgion of the electromagnetic spectrulil in which they aet.
So/ul;Oll ; As explained in the preceding exa mple, when radis,lion and matter are in
the rmal equilibrium, no net IIbsorption or emission occurs beeause th e total number of
absorp tion and emi!l4ion tral1Jlit ions pe r un it time is the same. Thi~ is indicated in '\[ewltllble ~I .. te
(upper [Mer [ev~ l)
Fig. 13-7 (a). Although the induced transition probability may be smaller th a n the
spontaneous transition probability, aOOoq)tion matches emission because of the large
population of the lo,,er level at thermal equilibrium. In the general case, in which radia.-
/
/
lion interacts with maller without necessa ri ly being in equilibrium, we have Optital
/ Stimula~
+
Emission rate _ IA zl B2IE(~}INz _ (I +~) N"
pumping

,,
V ITlIIIS; l ion

Absorpt ion rate BI 2E(.)NI B2I E( r ) NI

,,
where E(~} gives the energy distribution of lhe incom ing rad iation. If t he energy differ-
ence E2 - HI is sufficiently small, !!O that the ra tio b I tT is very small (as occurs, for E, ___L _ _-'-_
,/ Cn)Urni _tall!
example, in the microwave region at room temperature), Eq. (13.22) shows A2!/BZlt;(~) (Jo ..er J,....r ~vpl)

to be negligible compared with unity. Fig. 13-8. T hree-level laser.

"2 E, , -'"1
B,
! ! Several means have been de,iscd to overpopulate the uppe r level in a ~ teady fashion .
All these methods require some cxpenditure of energy, and the efficiency of a maser or
laser is thc ratio between the energy out pu t and the energy input. One typical method i~
~
2h. optical pumping, in wh ich encrgy is ~ upplied , eit her continuously or in bursts, in great
~

""""""
'V'J'J',,-
qUlllltitics simply to excite the system to higher ellergiea. All the system returns to the
groulld state, some exci ted atoms decay into St ates wh ich a rc Illctsst nblc, and these
states llIay casily become highly pop ulated rds,livc to !!Omc lower stale, as sho wn in
f;1 1.. "'I E, '\1 Fig. 13- 8. Stimulating radialion of frequellcy ~ _ (f:2 - CI )lh will then give the de-
sired amplification.
(n) (b) i\[fLSCCS and lasers are very useful because t hey l)roduce a very intense beam of co-
hcrent, 1lI0nochroms.lic radiation. The 8t lld en ~ 5hould fl'call t hllt when seve ral !!Ource!!
t'ig. 13-7. B:l.~ie ope rational prillciple of lascl1l alld mascl"lJ. radiate in phase {or wherently), the resultant &m[)1itudc i8 the SUIlI of the individual
 po

536 QUlln/!UIl Ila/is/jet (13.7 13.7) IItal ropacily oj lolid, 537

amplitudes. If all sour<:cs arc identical, we have
while for longitudinal W(WCS, which IItwe one degree of freedom, thc modes of
Resultant coherent amplitude - N X source amplitude, vibration nrc one-half as many;

where tV is lhe num\.l(!r of 8Ourc~. Since the intensity of the source is proportional to 4rV 2
U/(v) dl' = - ,- V dl'.
the sq uare of th e amplitude, we ha,oc that
'.
Itesultant coherent intensity _ N2 X source intensity. In each expression we usc the velocities of propnglltion v/ !lond /I" corresponding to
longitudinal and transverse waves, rcspcetively. The tOlnl number of vibrational
J( the number of sources is large, the IItimulaled radiation may be very intense. On the
modes' in the frequency range dl' is then
other hand, if the sources radiate incoherently, the individual intensities add linearly;
Ihal is,
Resultant incoheTCnt intensity - IV X source intensity. U(v) dv = U/(v) dv + g,(v) tlv = .11rV (~ +~) v 2 dv. (13.23)
~" /'/

Therefore, in masers snd lasers the ~timuillted, coherent, monochromatic radiation is

very intense, in comparison with the spontan C'Ous im::ohcrcnt radiation, which is called
noi36 in these devices. Due to the strong predominance of induced transitions, the noise
is relatively smaller in ma"Cl'lI and 1llSCrs than in conventional amplifiers nnd oscillators.
Maser nmplifier6 arc used whenever vcry low noise is of prime importance, such as ill
radioastrollomical work, satcllite communications, and microwave spectrometry.
In a continuous medium there is 110 limit to the totnlllulllber of vibrational modes.
But in II solid, which has nn ntomic structure IUld contnins N atoms, any vibra-
tional mode must be described in terms of the 3N pOSitional coordinates of the
atoms. This therefore imposcs a limit on the (olal n\llllbcr of independcnt. modes
of freedom, which must be cfjunl to 3N. T his in t.um imposes a limit Oil the maxi-
mum vibrational frequency becnuse 11'0 must have, u~ing Eq. ( 13.23),

1', 1"
13. ? lIe ll' f~'npflf'lt" tIl l!i flllf/M
3N = g(v) dv = 11rV ( ~ + ~) v 2 dl'
As explained in Chnpter 6, solids nrc regulnr aggregates of Inrge numbers of ntorlls o ~/ v, 0
(or molecules) held in their posilions of fixed e(luilibrium by Slrong cohe.nve forces 0'

~_lf +.=..?) .J!,

resulting from their electrical interactions. The only individual motions of the
atoms nre small vibmtion8 around thei r e{luilibrium positions. But the COUI)lillg
between atoms is 80 strong that you cannot.set onc atom ill vibration without dis.
turbing the nenrby atOIllS, and eventually the whole solid. Therefore we must
consider collective vibmtiollal excitations of the solid, similnr to those which were
considered ill Exnmple 6.2 for a linear lattice.
These collective vibrations sct UI) standing waves in the solid. Their freQuencies
depend on the shape nlld size of the body, and in a way are similar to standing
waves in II. cavity. Although the possible frequencies have a discrete s pedrurn,
their spacing is very slImll if the body is relatively large compared with atomic
dimensions lind the Spectrum may be a..sumed to be continuous. These standing
waves have the snme nnture as elastic waves propagated through 1\ solid, and
therefore their propagation velocity is the same as the velocity of the clastic waves,
also cnl!ed the l'e/ocity oj aoulld.
There lire two kinds of clastic W!loVCS ill a solid: longitudinnl nnd trMlsversc.
They prOI)ngate with vclocities ~l and ~I, respectively. To obtain the number of
different modes of vibmtion in the frequency range bet.lI'een II and ~ +
till, ex-
I)resscd as (/(11) d/l, wc IIlUst coun t the longitudinal and the tmnsvertle modes
sepnrately. Thus for transverse waves we have, using Eq. (13.18) wilh c replaced
by VI!
811'V 2
gc ( /I ) d/l = -,- /I dv,
'.
"3
3,\' = bV (13.24)
II~
which dctcnnincs the cutotT fre(lucncy Yo. (The e"iste!!ce of a cutotT frequency in
the vibrations of a crystal lattice was discussed in Example G.2.) Using Eq. (13.24),
we may write Eq. ( 13.23) in the fonn
9N ,
U(v)dv = - v dl'. (13.25)
':
The I)roblem wc::re discussing here is very similar to that of standing electro-
magnetic waves in a cavity. That. discussioll gave ri:;e to the concept of 11 I)hoton
gas introduced ill Section 13.6 for nnalyzing bl:\ekbody rndiation. We lIlay thus
associate with the vibrational modes of the solid, which of necessity are quan-
tized, a phollon !las composed of "particles~ or phonon.'! of energy 1Iv. The conee p~
of phonon was introduced in Example G.2. Since a ll !)hollons arc identical and
since there is no limit to the number of ph onon~ in the ~a!lle euergy state, we may
ex!)Cct that phonons in thermal equilibrium obey Bo!;C-Einstein stntistics. Also
the number of phollons is not fixed, since their !lulliber may increa.sc or decrease
del)Cnding on whether the energy of the modes of vibrat ion is increased or decreased.
Thus we must use Eq. (13.15), setting a = 0, as wc 1)l'cviou!!ly did for the photon
gas, and rel)lnce (J; by g(v) dv, given by Eq. (!3.2.i ). T he number of pbonons of
encrgy E = }IV in the frequency range betwcen v and v + dv and in thermal
 po

538 Quolltum I/o/illiel (13.7 13.7) lI~al (apocily oj rolid, 539

T ,\IJI : 13-3 De b)'e T e m perat u res of So m e Soli d.'! c.

If
Substance eo, oK Substance 9v,"K ',------------------.--------------
,I, 225 G, 366
A" 165 Na
Ki
IS'
.56 A.
C (diamond) ISOO
C" 339 p, m AI
0 C (gTa phite)
0 AI,o,
equilibrium \\ith the solid blticc at temperature T is then
K CI
2
d _ "(II) dv 9N 11 dll
; 11 - i'/IrT _ I ,,~ 1
~O"----,OO.5'---C,\;.O-----!...,---",I;;.o T19()
i'liT _

T he total vibrnliollnl energy of the solid in the frequency range d" is t-ig. 13- 9. Heat capacity of 8. crystal lattice 1\8 n function of the tempcrature.

'. ,
9Nh 1/3 dv
dU .. hv dll = - ,- h./IrT It may be noted that at temperatures of the order of eo or lrrrger, the herrt
capacities of all substances practically aLtain t.he value ~R, a result. called t he
and the total vibrational energy of the solid is Dulany-Petit law, since it was first noticed experimentally by these men in the
nineteenth century. T his is also in agreement with the principle of cq uipartition
1'0
U ..,.
1
o
'0
h/l dn = -,- ~.ll<r
"oOe-
9Nh ,,3 d" of energy, bec:mse for kT hvo = ke D, the vibrntional energy per degree of
freedom should be 2(;k T) = kT, and for the 3 degrros of freedom of each atom,
3kT. T herefore
We should add to ,hii:! energy the zero-point energy associated with each of the
modes of vibration. However, this energy is temperature independent and is of no
U = N (3kT) = 3kNT = 3sllT,
conc<!rII to us here. The hent cap.'lcily of the solid at constant volume is then corresponding to C y = 3R, in agreement with the Dulong-Petit law. Obviously
substances whose Debye temperature is much higher thall room temperature
, _ .!.
C, - s iJT
(au) = 9N
l'~kT2
Ah21"0 ,,4i,/kT
(l,/I:.T _ 1)2
dl', (13.26) deviate substant ially from the Dulong-Petit law Ilt such a temperature.
Y At this point we should consider whether, in the special case of metals, we
should take into account the energy of the free conduction electrons wherl we are
It is convenient to define the Debyt /cmperaltu"e eo as keD = '1110 or computing the heat capacity Cv . We must recall that free electrons follow Fenni-
Dirac statistics and that the equipartition of energy applies to them only at tem-
II) = /lvo / I.-. (13.27)
peratures for which k7' f., where fr is their fe rmi energy, or T f.r/ k = Sr,
The vrrluc of II) for somc solids is givell in T able 13-3. where a r is the Fermi temperature. But when we examine the values of f.' and
ncclllling that kN A = R f\.nd setting x = IIY/k7', we Illay writc Eq. (13.26) in a., given in Table 13- 1, we sec that the remli temper:\ture is so high that a.,
the simplificd form only a few electrons are excited when the metal is heated rrt temperatures used
' lOD,r 4"
in laboratories and industry. T hus electrons contribute n. negligible amount to
Cv '" 9R (e7'o) 0 (ez x e 1)2 dx. (13.28)
the specific heat of metals, We must note, however, that at. very lOll" tempera-
tures, close to absolute zero, when C y is also very small, as seen in Fig. 13- 9, the
electronic contribution to C y is relatively important. At these temperatures
T hc grallh of Cv IIgainst '1'/90 is indicated in Fig. 13-9. This theoretical.curve the very fell' electrons that arc excited above the Fcr'mi level EF contribute
is followed ill n sUlvrisingly accu rate way by most substances, :l8 shown III the to the internal energy an amount lurger than the energy of the collective lattice
figure by the experimentlll points. vibrations.

L
 540 Quall/um IfIlJilli" (13.8 J3.8} The idtal gas ill quar,/um f/a/idies 541

1:J.8 Tht' ",,,,1 t;OJf In flunnillm Stalistic l!I Introducing the value of e-I> as given by Eq. (13.30) , we finally obtllin
All particles follow either Fcnni-Dimc or Bose-Einstcin statistics. Therefore even
U = :J.kNT ( I - - I N )
an ideal gas should be analyzed from the point of view of quantum statistics. 2 2& 12 -Z - ... . (13.31)
Let us liTl3t consider nil idcni gas composed of particles that follow Bose-Einstein
statistics (which is the most oomm'on situation because molecules have either zero Whe n we compare this with the cbSli.ical or ~ IllxII'ell-Boltzmann idetl.l-g..'\..<; result,
or integml spin). The number (in of molecules with energy betwccn E and E: elE + U = ikNT, we see that Ihe qUrll1tum efTect in llosc- Ein..tein sllilistics decreases
is given by Eq. (13.15), with !I. 1"C1)laccd by the energy of the gas.
T he pressure of the gns (see Example 13.7) can be shown to be
4 1'(2 ')'"
g(E) d8 = h~ dE,
11' 81/2
p = kNT
l'
(I __2M21_ ~Z _.. .) ( 13.32)
which is E(l' ( 10.39). Therefore

<I 'lrV (2 In3) 1/2 __E~'_"_'~d~E,- and thus we sec that, in Bose-Einstein l't!ltistics, the presure of an ide:ll g3S is
(h~ = h3 also less tb:ln the pressure of a classical (or ~llIxwell-B oltzmunn) ide:ll gHS.
T he departure of a quantum ide,'\ gas frolll :i elHSlIical ideal gns is called gas
degeneratiQIZ ("degeneration" as used here has no relation to tho degenerncy of
If we set x = B / kT nnd recall Eq. (10..10) for the partition func tion of an ideal
quantum states). Observing that N IZ is proportional to (N I V) 1'-3/ 2, we realize
gas, Z = Jf{2'11"mkT)312/h3, we obtain the total nu mber of molec ules as
that the degeneration of a gns becomes more illlportnnt at low temperature and high

N
-_ 2Z
..r;.
1" Xl12dx
0 e"+1 - I
.
(13.29)
Jen~ity, conditions which occur ncar the condensntion p,oint. For most gases at
ST P, we have that N IZ is of the order of 10- 4 , and therefore gfl...~ degeneration is
negligible, showing that. i\lll.xwell-13oltzmunn stntistiCi! can be \I.'>Cd safely in such
gascs.
Hccalling that in Bose-Einstein statisties a is positive, we have
T hc two lightest gases that follow Bose-Einstein statistics arc 1-12 and helium.
(8"+" _ 1) - ' = e--Z( I - e--,-I = e-<>(e-" + e--o- 2" + ...), For Hz at its normal boiling point, 20.4 1(, thc value of N IZ is 0.84 X 10- 2 , and
for helium al. 4.2"K, the vulue of N IZ is 0. 139. T hU:l helium is a gas in which.
Bnd substitution into Eq. (13.29) gives us degeneration should produce observable cfTccUl. In fact, some I>cculillr behavior
of helium ill its condensed phase, known as 1'le-lI, has been /\SCribed to complete
Bose-Einstein degeneration.
N - Ze- (I + 2;12e- + ...) . In the case of an ideal gas that follows Fermi-Dirac statist ics (such as mon-
atomic hydrogen), the results are (Iuite sirllil:\r. lI owevcr, we N!i:al! that in Fermi-
As a first approximation , we lIlay write e-" = N IZ, which is the sume result we Dirac statistics a may be either negative or positive, nnd the refore the cases
obtained in Section 10.3. As n second approximation we Illay write a > 0 and a < 0 must be treated .separately. We shall not elaboratc furthe r on
this case. We point out, however, that although the pressure at the absolute zero
, of an ideal gns that follows either ~raxwell-Boltzmann or Bose-inst.C:in statisties
is zero, the pressure of an ideal gas that follows Icrmi-Di rac statistics approaches
( 13.30) a finite val ue ncar the absolute zero; i.e., thcrc is II zero-point pressure. T he rea-
son for this ill thM, even at absolute zero, an M'>Cmbly of ferrnions hus a zero-point
which allows us to obtain a as a function of Nand T. The total energy of the gns is energy U = lN E ~' (see Example 13.2). Hecalling Eq. (11.37),

1. , 1"' 312 d(/ = T rlS - pdF,

2Z I.:T x dx
u= o
J~dn= --
..;; e"+"- I
0 we hnvc, when the entropy is constant, /IV s = - p d l' s. Hence

"" ';1.:7'Zc- (I + _ 1-
2~a
e-Q + ...) . p ~ _ ('U)
av ,. (13.33)
 po

542 QUOlllum Iialil/iu (13.8 /3.9) Compari&Oll oj Ihe Ihrn Ifll/i,lie, M3

Therefore the zcr()-point. 1>!"CSSure of n system of fermiolls is and hence is ~lightly larger than the diSllical ideal-g:l.!l pl"CSl!ure. For negative (l", which
holds for low lcmpcraturcs, Ihe pressure is

p = ~ (~i,)8 = -iN~~' p - ~NtJ'[1+fuo-12 ('T)2 ...J.

2

5 V tJ'
Bu L from l!:q. (13. 10), we have In E.. = - ; Iii I' + Cj llCnce CJE ~'/CJI' = -2E.-/3V.
'!'IIis gives
I:'.~I ( :olllpuri14on fll tiff' Thrf'f! Slnt;14tiC14
2 .N t F
( 13.3-1)
P="5v I n thc previous section we SAW th nt quantulll effects nre rcl:\tivcly snmll in ideal
gllSCS at low concentration and high tempe ratures. We shull now compar e t he
for the zero-l>oint pressu re of a Fermi-Dirac gas. th ree stal istics to de termine Ihe cxtent to wh ieh they givc comparable results.
H ee:\lIing Eqs. (10.9), ( 13.5), a nd (13. 14), that is,
f; X /IMI' I 13.7. Pressure of an ideal gas in term.'! of the illternal l"llcrgy and the
volume. (a) M axwell Boltzmann, nj = g,-e ..... - A, /IT,

$ol" , io/I: Wc recall that, acco rdillg to Eq. (13.33), th e pressure of a system of particles
,;
may be computed by p - -(CJU/iJV)s. But U - :E;lI, E,. Now in a procC!lll at con-
(b) F ermi-Dirnc, Iti = e,,+;/IT +
stant entropy, the occupation numbers II, must remain constant since, as explained ill
Section 11.9, a change in ent ropy (or heat 1I.bsorption) is assoc iated with a change in the (c) Bose-Einstein, n, = gi
e",+ F. ;lkT
II;'S. Hence (iJU/iJV)s - :E, 11,(iJf:JiJt'), and
wc sec that t he three C!ln be writlell in t he form
(13.35)
gi + .J = e,,+K,IIT
n, '
AMuming that the ideal gas is composed of noninteracting particles in a cubical box of
side 0 and \'olulJ)e I' _ a3 , th<, <'lIergy levels are given by Eq. (2. 17), where .J = 0 for )' Iaxwell-Boltzmann, - 1 for Fermi-Dirac, tind + 1 ror Bose-
E instein stntistics. We can c[carly sec that if gil!!; 1 or if II, (li, that is, for
diluted systems, then the three statistics give practically identical res ults. This
is true at high temperatures (beca use of the incre:lSC of a with temperature),
which gi\'l'~ Therefore, except aL very loll' temperature, we mny neglect most quantum-
,.
2 .,.. f,- 2 Z 2
sl!\listical effects. This justifies t he usc or ~ [ axwell-B oltzlllanil statisti cs in m(lny
--3"_mV5/3(Sl+i\"2+ Na) inst an ces.

Substitutillg thi3 result ill E(I. (13.35), \\'<' find, for the pressure of the system of nOIl-
Ilf"f'rf'Rf"f'14
inleraelillg particles,
I. ~Thermodynami cs and Quanta in 1'1:lllel.;'$ Work, ~ ),1. Klein, I'ltl/.ie. Todoy, NO"em-
2" I1,EI 2 U ( 36) ber 1966, page 23
P-"3 L:' v - j V ' 13.
2. ~E\"olut ion of .\Iaser! and La.scrs,~ B. Lengyel, A. m. J. Pltl/" 31, 003 (1966)
For an ideal gal! which foUow~ .\bXllell-Boltzmnllll stat isl ic~, we ha\'e 1/ - ikN T, find 3. " Hesource l.cltcr .\10 1'-1 on :\11\'!('r! and on Oplicall'umt)ing, II. '\ I ~, Am. J. P ity,.
henee p _ kN1'/1', in agreemcnt wilh Eq. (1 1.16). For a Bose-Eillslein ideal gas, "c 32, 58!) (u)IH )
must usc Eq. (13.31) for V, obtninillg thtl rC5ult previously stated in Eq. (13.32) for p. 4. SI(lli.li.col T hermodYl1amic" . $chrOdinger. Cambridge: Cambridge Unil"Cfsity
l~or IL Fermi-Dimc ideal gfl~ fit absolute zero, V - jNfF and p - iNfr/ I', whieh is the I'reSll, [9(i4, Ch:"ptcr 13
valuc given in Eq. (13.31). A~ tcmpemtl1re~ different from absolute ~cro, the pressure
5. Slali.lical Ph.ysic., G. Wannier. New York : J ohn Wiley, 1966, Part 1
depen ds 011 the sig!! of (l". For positive (l", which holds normally Ilt \'Cry high tempera-
tures, the l)reSSUTC of a Fermi- Dirac id<'1l1 gas i3 6. Fllndflmcnlal. oj Sia/utical ThtrmodYliamicl, R. Sonntag and G. Van Wylen. Kcw
York: John Wiley, 1966, Chapter! 7, 8, and II
7. Til, Ftl/l1mal1 !.(lIre. ill PIty.i.eI, Volume 1, R. Feynmall, It. Leighton, and .\1. Sands.
lteMillg, '\Iass.: Addi;;on-W<,sl<,y, 1963, Chaplcr! 41 and 42
r ..
544 Qmw/um '/f1./i,/ic,
l \3.1 The Fermi energy vade!! wilh the
tempemture aeeording to the cxwe"lSion
where" is the value at 7' - 0, given in
Table 13-1. Show that the correctil"c term
oorfe!ponds to a change of I % in t~e Fermi
energy at II temperature T - "'3 e y/5r.
Estimate this tcrnpenllure for Ij()tl1C of the
metal! given in Table 13-1 aut.! cOllc!udc
to what extent one can a..'!.~ umc that the
Fermi energy T('mains oonstllut between
absolute zero and room tcrnpl'rn(urc.
13.2 Find the lwcrage vclority nnd the
average energy of clcclrQn~ at OOK in II.
metal having 10 22 electrons per em a.
i3.3 Show that the number of fcrlllions
wilh a velocity between v and v dv at a+
temperature Till
dN
13..1 Show that lhe number of fcrmiona
II-itll II velocity whose OOffil)(lllcnts arc be-
t,,'ee n to. and v. + dv., v. and l'. + d!'., and
+
" and I'. dill is
13.5 Show that the number of fcrmion~
with a component of velocity n.long the X-
axis betwceu v. and II. +
dll. is
,
_ 4:rVm , [(.,, _ ... :/21/kT + I[ dx.
dN. h3kT n e
[flint: Use the integralS; (ae' + 1) - 1 dx -
In (1 + J/a).J
13.6 Using the result of Problem 13.5, de-
rive Richardson's equation ( 13.1 1). [flint:
Use the allproximation In ( I + :1:) - I ,
when I is small.]
13.7 Plot the HichardllOn-Dushmall C<l ua-
tion for therm ionic elll is.~ion ,,~ 1\ funflion
of kT/ t<I>. Show that the tCIIlIJ('rature at
which thermionic emb:;ion is U1ll.xirnuUl i~
T _ t<I>/ 2k. E~timstc the value of Ihig
temperature for OIOme of the metals gh'en
in Table 13-2.
13.8 When ).la_~well-Bolt~msll11 8tll.tislics
is used instead of Fermi-Dir:!.c statistic!J lO
anslyre thermionic curre nt den ~it y, the
expre!!Sion obtained is
i _ .-I T! {2e-<,kT .
(a) Derive this equat ion. (b) Plot) agllinsl
kT/ e1> and eompn.re with the plot of the
Hichn.rdoon-l)llshman e()ualion, ass uming
in both case..thatq, - 3eV. (e) E~timale
the temperature e - ~/k for some metals
/Lnd decide whether both equations gh'e
clearly distinsui~hable results at room
tcmperatures.
13.9 Sho"' that the constant .-I in Eq .
(13.1 1) has the theoretical vallie of 120 A
cm-2 "K-z.
13.10 }-'roOi Ollr discussion of the Jloten-
tial stcp in Chaptcr 2, "'e kno ..... that so mc
eie<:trons Iha ~ resch the surfll.te of n metal
should be reflected back i .. to the metal
even if their cnergy is largcr thnn~. (a.)
l\lodify Eq. (13.10) to t:lke this cffect into
ae<:ount. Justify the fact that the experi-
mental ,"alllcs for A (Table 13-2) are less
than the theoretical valuc gh'en in the
previous problcm. (b) Find the reflection
coefficien t for cesium and chromium.
13.11 For what "allles of tha energy E,
greater thnn O ~", is II; _ !i',~-(K- .... /t T
within 10% of Eq. (13.S)?
13.1 2 For the encrgics indicated in Prob-
lem 13.1 I, we can write
S... V(2m ')'" ,,11
2_(Il _.v)/~ T
N(t1dE - h3 ,e
instead of Eq. (13.9). 8ho ..... that the num-
ber of electrons per unit volume with
PrOOl~nu 545
energies equl\l to or greater than a certain expression for the hea t cllpacity is
value Eo larger than Of is
,
8:rV(2m ) 'fl.TkT
The dependellce of Cr on 1'3 at low tem-
h' '
XII..'TJ I!Z['Z - r
er"T EoJ+ ,"112-.D1~T)
_Of:
peralUres has been I'erified experimentally.
[lIint: Set I _ en/ T in Eq. (13.28) and
note that the upper limit call be equated
l/lint: Hcfer to Problem 10.21.] to infi nity.]
13.13 lTsing the result of I'roblem 13.12, 13.20 From the following experimcntal
find, for II metal with Of _ 2.00eV and data for nickel and silver, determine the
4> - 3.00 eV, the ratio of the number of Debye teml>eralUre of the two materials.
electrons Iltr unit volume having an energy The atomic mll.SSCS are 59 and 108 and the
equlll to or larger thl\l) the work function
dell!iitie~ arc 8.9 X 103 kg m- 3 and 1.05 X
at room tempernture to the number at 10~ kg m - 3 , reSI>ectively.
1000"1< . [I/int: See Problem 13.11.)
13.101 Find thc number of photon.~ per
T, OK Cr, cal mole- J "1( -1
cubic meter having a frequency between
~m . . and 1.05v",.~ in a blackbody radiation
field at 300"1\, whcre v", .. corresponds to
N; A,
the reak energy density. 2 0.0041 0.00013
13.15 Assume that photons behave as
classical O!!Cilla\ol"!:! ..... ith an avcrage energy
,
4 0.0080
0.0132
0.00201
0.0089
of kT. Obtain the ellergy density distribu- 8 0.0186 0.0242
tion; this i3 the Hayleigh.Jeans law, ..... hich 10 0.0238 0.0--178
12 0.0301 0.0830
..... as mentioned in Problem 1.9. Why does
14 0.0379 0.134
thi~ ass umption give the same ene rgy dis-
0.0--183 0.201
tribution when we make the lo"-frequeney
approximation of Planck's radiation law? "
13.16 Assu me that Ilhotonsobey Maxwell- 13.2 1 Using the graph in Fig. 13-9, csti-
Boltzmann statistics. Obtain the energy
density di;ttribution. This is lhe Wie .. law,
mate the heat caJl8eity 8l room tempera-
1\"hich ""as mentioned in Problem 1.9. Why
ture of (II.) sodium, (b) gold, (c) copper, lind
(d) diamond. COlilpare with the experi-
does this assumption ghe the n me encrgy mental values.
distribution ..... hen we make the high-
13.22 (a) COllsider a sys tem composed
frequency approximation of Planck's radi-
of N harmonic oscillatol"!:! of frequency 1',
ation law?
following l\1axwell-B-oltlmann statistics.
13.17 lising Tablc 13-3, find the ma.~ i Find the heat capacity of the system at
mum frequency and minimum wavelength
for l)honolls in germanium and diamond.
constant volume. (b) Thig model WIIS
used by Einstein in the fil"!:!t attempt to
COIllJlare with the wal'elength of neutrOIl ~
Ilt room tcmperature (300" 1().
apply st.'\tistical methods to cxplain the
hent capacity of solids. Introducing the
13.1 8 Filld thc ratio of spontancoUl! emis- constant e~ _ h~/k, express C~ in terms
~ion l)rohability to induced emi>l!lioll prob- of e rJ T. Compare with the expression
ability I\t 3001\ for (a) thc microwal'e for Cv in the Debye theory. Analyze thc
re)lion, v """ 10 13 li z, and (b) the optical way that the theorics can be dilTerentiated.
rrgiOil, v "" 101~ Hz.
13.ln Sho. that aL temperatures vcry
[Note: Ein ~t cill' s theory ..... as discarded be-
cause of thl! fnct that it was illll)QSSible to
I
small compared with en, the Debye find a value of fh: for each substanee that

Quail/urn ,/a/islie,
would gil'e results in agreement with exper-
iment at both high and low temperatuTe!.)
13.23 Sho"' that the heat capacity at CQII-
stant \'olume of an ideal Bose-Einstein gil.!!
is gil'en by
(N)'
+ 3M2 Z+"" 1 the electron gas in a metal. In view of the
where Z is gil'en by Eq. (1 0.38 ). Estimate
the effect of gll..'i degeneration on the heat
capacity of helium at room temperature
and at I atm of pressure.
13.2-1 ShOll" that the heat capacity at
eonstaut volume of an ideal FcrmiDirac
gn is gil'en by
(kT) [1-"10 (kT)'
C" - ;UIr- -;; 3r' 1
-;; + ....
From this !'elIult estimate the heat capacity
due to freecleetron~ in a metal. Verify that,
e.~cCI)t at I'ery low temperatures., the elec-
troni c heat capacity is negligible compared
with the lattice hellt ellpacity as given by
the Dcbye theory.
13.25 Sholl' tll!1t the temperat ure at
which the lattice (l1Id the electrollic heat
capll.citie8 Ilre equal is
T. _ (5a~/2411'2e~)I I ~.
E~timate thi~ temperature for some metal~.
Show thllt at temperatures lo"'er than T.
the electronic heat capacity is largcr than
the lattice heat cApacity, while the /'flvel'$C
is true for temperatures highcr than T.
(I/illl: Use the result of Problems 13.HI
and 13.2-1.1
13.26 From the expl'ession gil'el1 ill Prob-
lem 13.2] for t he heat capacity of nn ideal
FermiDimc gas, show that tht) entropy of
the gil.!!, whcn ovlkT I, i$
s _ (.V n.-'/ 2 )(kT / f1')
X (I _ (1I'2/ IO )(kT/ _1')'+" '1.
p
13.Ti Estim!l.le the value of ,v/ Z for N2 (/l int: ~'or the 13.!!t relat ion, see the elCllTe$- rela l ions reduce to Eq. (10.24) and Eq.
at STP, "'here Z is the ela.ssical partition sion for S given in Problem 13.29.1 ( 11.28), respectively.
function. Determine the rd:ltil'e ellect 13.31 Show that, whell 0: is very small, 13.32 Show that the partition funct ion or
of the gas degeneratiOI\ term in cxpreS$ion Z, - ,-aZ, where Z, is the qUAntum a photon gas is Z _ (811'5 V/ 45)(kT/ hc)3.
(13.32) for the preililure of n Hose-Einstein partition function defined j(l Problem 13.30 T hen show that the total energy of a photon
gas. Also de termine the ellect on the hent lind Z is the classical partition function ga~ is U - (811'5V/15)(A:T) ~ /(hc)3 and
Cnl)i\city of this gil.!! (givcn in Problem defined in Eq . (1 0. 22). Show also t hat the that the entropy i~ S _ 4U/ 3T. (IIint:
13.23). first relation in Problem 13.30 reduces to Note thatfo'" ;t21n (1 - t- I ) dz _ - T 4 / 15 :
13,28 }o:Slimate the ~ro-point pressure of an ident ity, while the second and third use the relations gll"en ill Problem 13.30.1
I'aluc obtained, explain how the electrons
remain inside the metal.
13.29 Show that the entrOpy of a sys tem
of partides in quantum ! IMii lics is gil'en
by
u
S - 'T + akN
k 1: g, In ( I e-a-E,.,tT),
where the posith'e (negfllh'e) sign corre-
sl)()nds to Fermi-Dirac (Bose-Einstein)
slatisties. Also shOll' that in both cases if
a is \'ery small the expres:>ion for S rcduce~
to Eq. (11. 28). lIill/: Fir.;t show, u~illg
either Eq. (13.3) or ( 13.13), that
13.30 In quantum s lati~t ic~ the p1lrtition
function is defined as
where the positive (ncgatil'e) ~ rgl1 rcfers
10 Fermi-Dirac (nose- Einstein) statistics.
Show th:lt the total numiJ1)r of ]11lrtieies,
thc total cncrgy, and the en t ropy arc ginn
by
N _ -(iJZ./OO)T,
U _ kT2 (iJZ.jiJT).,
S - kT(oZ,/oT).+ aU + kZ.

, APPENDIXES
 APPENDIX
SUPPLEMENTARY NOTES

I. Helmivi.t.ic lt1eehanie8
Let us consider two inertial observers, 0 and 0', in relative motion. GiVCll that v
is the velocity of 0' relative to 0, then t.he velocity of 0 relative to 0 ' is - v. We
a
shall orient the axes XYZ and X'Y'Z' attached to and a', respectively, so that
axes X and X' aTC parallel to the relative velocity v and the Y and }" axes are
parallel to each other. Then axes Z and Z' are also parallel (Fig. A- I).
Suppose that When 0 and 0' are coincident a light signal is produced at the
common origin. If c is the velocity of light in vacuum as measured by 0, after a
time t observer 0 sees that the wave front of the signal is a s phere of radius r, so
that whe n the wave reaches point A we must have r = ct, or since
r2 = :t Z + yZ+z2,
then
(A. l )

It is accepted as a basic principle that the velocity of light is the same for all
inertial observers. The experimental foundation of this asse rtion is based on the
y ) .,

.H.r. U. l, I)
i (.r ', y'. :'. I')
,,
,,I
~ :
__ '..,
t" II' , I
I
-- ",', I~ X
.... " ",
.... ,
I
I I
I x'
X' '" I I
'~.V
Fig. A-I. Frames of reference in uniform relative translational motion.
551
 55' Ap~ndi~ Apptlldix 553
experiment.'! of .'Ilichcll<Oli and '\torley, who measured the velocity of light relative This set of relations is called the Lorellu trails/ormation. Beeuuse of the relation-
to the earth in different directions, and found that the result. is the SUme irrespec- ship set up bct.wecn Eqs. (A. I ) and (A.2), we 8Uy that a Lorentz transformation
tive of the direction of I)ropagatioll. Therefore, if observer 0' also lI,ca,surcs the Icaves the quadmtic form ,2 y2 + +
Z2 _ c 2t 2 ... 0 invariant when we p3SS ovcr
velocity of light as c in nil directions (so that. to 0' the wave front. of the signal is to the primed coordinates. The Lorentz trnllsformntion reduces to the Gulilcan
also a sphere), he must write, when the light wave reaches point .4, that r' = ct' o r trnnsformatioll when v c.
If 1110 is the Illnss of a particle when it is at rest relative to an ob:server, the
, (A.2)
Illomentum of the particle whcn moving with velocit,y v relativc to the observer is
~olc thnt obl<crvcr 0' 1101. only measures different space coordinntcs ror
point 11
from lh ()!;C thnt 0 mct\Sures for point A , but for him the measured time of arrival (A.5)
of the ligh t signnl at tI is also different from the time measured by O. This is
where
required if the velocity of light. i~ to be t he same for both observers.
The next task is to oblnin n tnl1lsform:ltion relnting the qU:U1tiucs (x, y, f, 0 and (A.6)
(x', y', f', t') mellSured by 0 and 0' and giving the space di,;placement and the
is the elTeetive mass of the particle relative to the ob;scrver. Expression (A.5) rc-
time interval of two cvent!>. which arc: ( I ) the emission of a light signal when 0
duces to the nonrelativistic expression for momentUtll when v c.
and 0' were coincident, and (2) its arrival at :\ , with both set.s of quantities sat- The force 011 a particle is defined as
isfying Eqs. CA. [) lind (A.2), respectively. The symmetry of the problem suggcsts
that y' = y lind z' = z. Also, :<inee 00' = vi. for observer 0, it must be tlmt dp d ( 1II011 ).
x = ~t for x' = 0 (point 0'). Thi;.j suggests thllt we set x' = k(x - vt), where k F = dt = dt vI v2/c'
is a constant to be determined, Since t' i.~ dilTerent from t, we may also 1181!Ullle that
t' = a(t - bx), where a und b arc constant.! to be determined (for the Galilean To compute the kinetic energy of u particle, we recall thal II = dr/dt and
tf1msformalion, k = a = I lind b = 0) . .'lInking aUlhcsc substitutions ilL Eq. (A.2), vdv = vdv. T hen
we have
1,'1<=

or, if we collect terms,

This equation, however, must be idenlieal with Eq. (A.I). Therefore I ntegrating by parts, we have

m,,' /. . 1110" du
EI<=
Solving these three equations for k, a, llnd b, we have vi V 2 /C 2 0 vI V1/C 2
, and (A.3)

Combining the first two terms with a eomlllon denominatol', lI"e may write
Hence the transfornmtion compatible with the invarinncc of the velocity uf light is
(A. 7)

y' = y,
(A.4 ) Therefore we IllUY say t.hat, as a result of the dependence of the mass 011 the veloc-
z'",. z, ity according to E<I. (A.6), the gain in kinetic cnergy of a particle may be considered
as a gain in mass, Am = 111 - mo. We can extend lhis interpretation to associate
 554 Ap~ndi;r;
Appmdb:

a change in mnss 6111 to Imy change in energy t.E of a system of particles. Both The similarity of Eqs. (A. 14) and (A. I S) to Eqs. (A. I) and (A.2) suggests that we
changes arc relnted by the expression Clln make the correspondence

(A.8) pz --t X, p,,-1/, P."'" :, ct - Ele

The quantity llloe 2 is called the rtal tfltTgy of the particle, and the quantil.y
moe
2
2
in the Lorentz transformation (AA ) for the space coordinates and the time in
order to obtain the transformation of momentum and energy; that is,
E = Ek + moe2 = .; ) _ v 2 /e 2
=mt: (A.9)

is the lolal tl!trgy of the pnrticle. The total cnergy of the particle, as here.defined, p~, = PM'
(A.16)
includes kinetic energy and rest energy, but. not potential energy. p~, =
p"
Combining Eqs. (A.S) and (A.U), we sec that E' = (E - vpz)fV I

(A.IO) If we have a system of noninterllciing particles, \\'e may write t.he total momen-
tum of the system as f' = L; P i and the total energy as
Using Eq. (A.5) to elimin!\te v in Eq. (A. IO), we have that

(A.II)
where M = L; m,'. Although in relativistic dynamics it is impossible to define
Sillee E' k = t: - lIIoe 2 = c vm ~c 2 + 112 - lIIue 2, when the vclocity is small com- the center of mass, we may still define a ccn ter-of-mass.vclocity or system velocity
pared with c (or when II is small compared with 1IIue), we have that v. according to Eq. (A.IO), by

Ek = _ 1_ p2 +~ ..L..+ ... , (A.12) (A. 17)

2mn 8 m~2
which reduces to thc 1I0nrclativistic formula Ek = p2/2111n when p moe
An interesting special cnsc occurs when the particle has zero rest mnss (rno = 0),
which is thc case for the photon and the neutrino. Then Eq. (A. II ) reduces to
E = ep p = E/e.
This resuil, substituted in E(I' (A.IO), gives I> = e. Hence n Imrticle with. zero
rest mass can move only with the velocity of light and can never be at rest III an
inertial system.
Equ:ltioll (A.I I) may also be written ill the form
In a frame of reference moving relative to 0 with a velocit.y 1>., the total momen-
tum of the system is zero (this is called the zero-momentum or C- frame of refer-
ence). This statement can be proved as follows; Suppose thnt. observer 0' moves
with velocity v relative to 0 in a direction parallel to /'. Then according to our
convention in choosing the coordinate axes, we have that Pz = P, P" = p . = 0
(A. 13) and P;. = P', P;. = P;. = O. Hence the first. relation in Eq. (A.16) gives
(A. IS)
If observer 0' is in thee-frame, he must have p' 0:: O. This requires that v = e2 P/ E,
which is equal to the velocity v. defined in Eq. (A.17 ).

p2 _ E2/C2 = _ m~2.
11_ Co/lillian"
Since P is a vector qunntity, with components pz, PM' Ilz relative to tho Xl'Z fmme
used by observer 0, we mlly write instead In an isolated system of particles (i.e., a system of particles not subject. to any
external actions or forces), the total momentum and t.he total energy, both referred
(A.14) to an inertial frame of reference, remain eonstnnt. These t.1I'0 conservation laws arc
lIot independent because, in view of the Lorentz transformation (A.16) for energy
R elative to another observer 0' Illoving with velocity v relative to 0, we nlHSt. have and momentum, the conservation of momentum in all inertial frames also requires
the conservation of energy. We shall now apply these conservation laws to the
(A. IS) analysis of collisions.
 Apptndil: 557

When two I)MliC\cs approach each olher, their mutual interaction changes their \1')
molion, I)roducing nn exchange of momentum and energy. We then say thaI. there
has been II ,00Ii';01l. In SOllle collisions (such as in nuclear and chemical reactiolls ) (1 1 '"fo 1'(' 1-.'( W)
the filial particles urc not idcntic:llio the initial ones. When the initial and filial "'1. /' 1' X I (I ) '"I" ' \< 8 1

(>article!> are the ~umc, the collil<ion is called scattering.

--
(2'
r
, In a collision cXI>criment, we usually kllOw precisely the motion of the p.'Lrticlcs
before the collision, since such motion depends on how the experiment has ~n
Collision
regioo
CoIliaion

prepared. For cXIl.Inplc, one ()article mny be a proton or au electron ac<:<:lcralcd III
an e lectrostatic accelerator uud the other particle lIlay be an alom practically at 120
"'2. 1'2. 1-:2 ...;, I~. I-.'~ (2\ "'2. I~J' 6 2 (3')
rest in the laboratory_ Then we observe the final slatei i.e. , the Illation of the twO 121
particles lit points far away from the region in which they collided (Fig. A- 2). On
the other hand if we kllOw the forces between the particles, we may predict the Fig. A-2. The total momentullI and Fig. A-3. Momentum and energy are
final slate, so [~ng tI.'l we know the initial state. Hence the analysis of collision the total energy arc conserved in all colli- conscrved even if the number of particles
experiments provides v:lluable information nbout th.e.interacti?n betwccn th: col- sions. is not.
liding particles. This is one of the reasons why collISIon expenment1! are so mter-
esting to the physicist. and we have an illelastic collision of lile first kind, also called tndoeryic. Whcn
Since only interllnl fOI'ecs cnter into play in the collision, both the momentum Q > 0, there is un increase in kinetic energy of the particles (or I~ decrease in
:lnd the tot:11 energy are conserv(.'d. Let 1' 1 and 1'2 be the momentum of each mass) lind wc have an inelastic wl/ision of tlte second kind, called txoergic.
particle before the collision and p;
llnd 1'~ be thc momentum after the collision. When more than two I)articles are produced in a collision (Fig. A- 3), the above
Conservation of momClltum requires that definitions bec<lme

(A. 10) (A.23)

Conservat ion of energy rC<luires th:lt When Q < 0, there is a minimum threshold kinetic energy of the incoming parti-
cles ncede<! to make the collision occur or "go." We may calculate the threshold
8 1 +8 2 "'" E~ + .6'2, (A.20)
kinetic energy in the L-framc (or laboratory frame) from the fact that the resulting
particles are all at rest. in the C-frame. T he expression for the threshold kinetic
energy was calculate<! in Example 9.3.
, (A.21) For nuclear reactions at relatively low energies, 11.11 particles may (in general)
be [reate<! nonrelativistically, so that Ek. = p2/ 2111. Let us consider the case in
By prollCrly handling Eqs. (A.19) and (A.2l), we may find th~ fillai mOI~enta of which a projectile of rest mass ml and momentum 1' 1 collides with a nucleus,
the p:lrticles in terms of the initial ones. The algebr:l., however, III generalIs rather called the target, of rest mass 1112 and at rest in the laboratory (P 2 = 0), as in
eomplicllte<!. Fig. A-4(a). After the collision the resulting particles move as shown in.Fig. A-4(b).
, Recalling that e ""Ek + llloe 2 , where El is the kinetic energy, insleoo of Eq.
(A.20), we may write ,. ,.
Let us illtl'oouce a (IUantit,Y Q define<!
collision
ru; the change in kinetic energy during the 0
,
,,
/. . pf

(A.22)
m~~
I3efore MWr
Therefore Q is also equul to the change in rest energies during thc collision. If
Q = 0 kinetic energy is COfl!SCrvcd in the collision, and the collision is calle<! ,.) 1",
elastic: Whcn Q < 0, there is it dcerease in kinetic encrgy (or un increase ill llUWl) Fig. A-4. Relation between momeula relative to the lrframe before and after a toBision.
 *'
Ap~/ldix Ap~flJix 55.9

Conservation of momentum gives P I = p ~
P2 2 = (PI - p'i)2 = P~
Using definition (A.22) for Q, we have
+ Jl ~ or l' ~ = PI - p i. Therefore billiard balls, one initially at rest. Figure A- 5(b) shows the collision of two helium
nuclei in a cloud chamber; the incoming helium nucleus is an a-particle from a
+ p~2 - 2p1P~ cos fJ. radioactive substance and the t{l,fge~ helium nucleus is from the gas in the chamber.
I n both cases, the two particles move at right angles after the collision.
Another interesting case is that of a capture process in which a particle of mass
1111 and momentum I' I collides with a particle of mass 1112 at rest, and a single
particle of mass 101 results. Then PI = 1',If and Q "'" EUI - Bu. But

Hence
(A.25)
0'

Q= -
2 m~
1(1-+-1)., +-1(1- - -1)
m~
PI
2 m; ml
PI2 - 2JE..! cos.,
m;
The quantity - Q is the excitation energy of the resulting [)MUcle, such a$ the
excitation energy of a compound nucleus in a nuclear reaction. In most cnses
M "" ml + Ui2 and thus
RcmemberinIC that E. = p2/ 2m , we can express the above result as
(A.26)
Q = Btl (I + m:) _ Bu (1 _ m:)
m2 m,
_2V mlm'I,E.IE~1
m,
cos 8. (A.24)
The opposite or a capture process, which is called an explosion, occurs when a
particle explodes or decays into two or more fragments. This ta.kcs place, for
This result, known a$ the Q-equalion, has many applications in nuclear physics. exam[lle, when a grenade explodes, when a parUcle decays into several other
When the collision is eln.stie (Q = 0) and all the particles are identical (ml = particles, or when a nucleus undergoes fission. We shull consider the case in wh ich
m; = m2 = m~), the conservation of energy givcsp;2 + p~2 = pt while from the the particle, of m3SS m, is initially at rest ill the L-frame, which then coincides
. of momentum, P I = P I + p ", we have PI" + P2" + ?"
conservatIon - P I p , = PI
2
with the C-frame. If the particle divides into two fragments of masses ml and
Combining these results, we find that pi . P2 = 0, or P; is perpendicular to p~. m2 , so that Q = (Ill - ml - 11I2)C 2, in the nonreinlivistic approximation we ha\'e
Thus, in the L-frame, the two particles move at right angles after t.he collision.
T his may be seen in the photograph (Fig. A-Sa), which shows the collision of two 0= P I + P2 and

From the first equation we conclude that P I = - 1'2 or PI = 1'2. Thus the two
fragments move in opposite directions with momenta that are equal in magnitude.
The second equtltion then gives

, Q =-2 1('-+-1), I,
ml 1112
PI = - P"
2",

where", = fIII1I!2/(ml + 1112) is the reduced Ill!\&! of the two particles. lIencc
PI = P2 = (2",Q)I/2 and the two fragments move apart with well-defined mo-
menta. The kinetic energies of the particles arc also well defined, and are given by

(A.27)
'.1
Fig. A- 5. (a) Collision or two equal billiard balls. (b) Collision '"~
or two a-particles. In If the particles are trented relativistically, the result is
both cases, one of the particles W(UI initially at rest in the lArame; their momenta make
angles of 90 in the lrframe after collision (part (a) courtesy PSSC Phyticl, Deaton: m - m 2 + lII L
En = 2m Q.
D.C. Heath).
 560 AprtnJix 56'

Whell the initinl I>nrlicic divides into more than two fragmen ts, their momenta
and energies do not have Uni{IIiC values. The conservation C<I U:ltiolls arc
lind
, and these equations can be ~llti"ficd by SC\'cral values of I',. In the p..'lrticulnr C:lSC
of an explosion or decal' into thrcc frflgments, so that.
o >= P I + 1' 2 + P 3,
there is II. simple pietorilll 1I'11y of representing the pos:;:iblc distribution of I\IUmcntll
tllllOng the three part ides. We dmw nn C<jUiialcral triangle of height Q (Fig. A- 6);
the perpendicular dis lllnccs from any ])(Jint P to the sides of the tri:Hlglc give the
values of the energy of the three fragments in a given dccay, In lIdditioll, conser-
vation of momentum rctillires that the point P (in the nonrcl:\ti\'istic cal)() be
imsidc the circle of radius &Q in~cribed in the triangle (in the relativistic case, the
curve dcparts sl ightly ffom II circle). T his representation is called a Dalilz dia-
gram, and is widely used tl) l\.Seerlain whether a partieul:ir mode of decay of a
I)articlc correspond" 10 decay illto three partieles. For the proof (If our statement,
note that. 7)1 + 112 ~ {la, necessarily, and t hat. the three cnergies call be expressed
~ into t.wo frequencies, wand 1.01', whieh arc ntmost equal, so thnt w' - w is very
+
Hil "" PN = hQ r cos (I/> - t1r),
En = PM = !Q +
r cos (I/> V), + sine wave we have
8 u = PL - !Q +rcos l/>.
,.
mo tion. If we have a continuous harmonic 1\lIVe (or as it is sometilllcs said, :~
wave train of infinite length, :IS in the expressions given aoove), the wave has II
single walelength and a single frequency. But a wave of this n:lturc is not ade~
quate for transmitting a signal, because a signnl iml)Iics somcth ing that begins at
a certain time and ends at a certain bIer lime. That i!:l, the wave must have a
shape similar to lh:\t indicated in Fig. A- 7. A w:\\'e II ilh such :1 shape is called a
pulu. Therefore, if we measure the velocity with II hich the signnl is transmitted,
we are essentially implying the velocity with II hich this pull<C travels.
We may at first S-'ly: Well, this velocity is just the ph:\.OO velocity I> = wi"',
s.ince this is the velocity of l)rOpagation of the waves. However, an important
factor enters here. The wave or pulse depicted in Fig . .\- 7 is ,wt Il:Irmonic, since
its amplitude is not constant along the X -llxi". Thll.~ we must make n Fourier
analysis of the wave. "'hell we do, we discover tlmt it IIctll:llly contains sevcral
frequencies and wavelengths. Of eour8C, if the velocity of propagation is inde-
pendent of the frecluency (i.e., if there is no dispcn>iou), then nil Fourier com-
ponen ts of the pulse travel with the same spced, and we are correct in saying that
t he velocity of the l)ulsc is the s:lme a.s the phase velocity of the waves. Howcver,
in n. dispcn;ive medium each i'ourier component has its own velocity of prOp!lga-
tio n, and therefore we must examine the situa1ion more elITcfully.
For simplicity wc shall consider n ease in which the pulsc may be broken dOll"n
small. We shall also a.ssume that their amplitudcs arc the same. Then using a
= A sin (h - wi) + A sin (k'x - 1.01'/)
= A[sin (h - wI) + sill (k'z - w't)J
= 2A cos ~[("" - k)x - (w' - w)/J sin iHk' + .!:)x - (w' + w)t/.

, " Since 1.01 and w' ,\5 well as k and k' are :llmost e(IUal, we may rCI)lacc Hw' + 1.01) by
./ wand !(k' + k) by k, so that
".
= 2A cos Wk' - k)x - (w' - w)/J ~in (h - wi). (A.28)
./ Equation (:\.28) represents a wale moiion whose !lmplitudc is modulated. The
./
.,'<---"'-'-1"'-----1
modulation is given by the factor

2.4 cos ~[(k' - k)x - (w' - w)IJ.

Fig. ,\-6. Dalia diagram for three- Fig. ,\-1. WilXC pulse.
particle break-up.
This is indicated in Fig. A-8. T he modulatillg ntllplitude i1self corresponds to n
wilve motion prupugated with :I velocity
,... t;rmlp ""'m'lI" w' - w dw
Let. us cOlisidcr a harmonic IItwe which may be described by = A sin (b - wl) "g = k' _ k = dk' (A.29)
or by the complex expression = Aei(kr-w/l . This wave h:lS an angular frequeucy
wand wavelength X "" 27rlk. T he quantity v = wlk is called the 1JilalJe velocity. which is called yroup toeiodly. T his is lhe velocity II i1h II hich the ;)mplitude wave,
However, this is ll?t necessarily the velocity we observe when we analyze a wave represented by the dashed lines in Fig. :\- 8, prO]l:lgate~. If IIe remember tha~

!iliZ Appmdiz. Appendix !iliS

Therefore

(A.3I)

-- By successive differcntiation with respect to a, we obtain

Fig. A-8. Phase " cloeiLy and group velocity.

(A.32)
= kv, Eq. (A.29) becomes
3~
(OJ

d. [ o x ' e- "'dx = -- ,
B a~ (A.33)
v~ = p + k tlk' (A.30)
and so on. On the other hand, by dircct intcgration we have
We can obtain the SftIilC result if we represcnt the wave in complex lIotation.
If the ph:w:: velocity is illdcpcndcnt of the wuvelength, uu/ dk = 0 and v. = v.
T herefore In nundispersivc I11OOi:1. there is no difference between pho.sc vclocity 1"
,
xe
_~ . 1
11.1:= -
2. (A.34 )
:wel group velocity, us lI'e inferred previously. But in II. disl>crsivc medium the
groll]) velocity muy be larger or b'lllullcr than t he phase velocity. We may con- nn d by differcll tiation of Eq. (A.34) wit h l"esI>cct to a, II"C find thllt

1"
clude thell t hat the 111:\..-.:i1ll\l1l1 of the pulse in Fig. A-7 propngnlcs with t he group
velocity II" In (lualllum mcchanics a particle loct\.lizcd ill n region ~x is represented xe
a -<>zf
dx = -2
I
o 2a (A.3S)
by a wave I)..,\ckct, and the I)''lrliclc velocity, which is the 0(lui"a]cII1 of t he signal
velocity, is the snmc as t he grou p velocity.
Al though we have derived Eq. (A .30) for the case of only t,wo frequencies, it,
nlso holds true for the ease of II Imlsc cOl1taining frequ('llcics in the rnnge from 1". StirU"f,'N " 'flrm"l"
w - Aw to W + Aw. We must wllrn the render, however, that this matter is really I II Clmpters 10 and 13 the eXi>r~ion In x! ( whcre :z: Us an integer) is encountered
more COlll l)lex than our prcscnt ation indicates, and a thorough discussion of it. is sevcrnl timcs" When x ill very large, an adequate approximnlion for !n x ! is
beyond the scope of this book.
In :d = x In x - r, (A.3G)
' I;. Sf,,,u' IiHf!/'" Intt'f/rtdH which is called Sli1"lill!}'lJjoJ"lI!ula. T his can be prov(.d easily in the following \\"lIy:
In Ch:ll)ter 10 an illtegrnl of the form 1 = f:
e-<>~' dx IIppearcd. We shill] now
In x ! = In I + In 2 + JII 3 + .. . + In (x - I) + In x
evnlu:lte thi", integral. If instead of the va riable x, we use the symbol y for the
variablc of integrntion, we lI\a.v write / => f:
e-<>"'" dy. ;\[uitiplying these tll"O =

2:, Inx, only if x is :\n integcr.
expressions, wc h:lYe

But if x i ~ ve ry Iargc, we can replace the summation by nn integral without. grcut

error, and \I rite

Thi.~ double integra! CHIl be cOllsidered a."i extended over the first. quadrant of the III x ! :. h~ ln x dx.
S}"-pbnc. The l"e.~u[L of the double integral11lust rell1:l in Ihe /lame if, instead of
rcctuligulllT coordinlltes (x, y), we U!<C pobr coordinates (1", 8). Sillce..&2 +
y2 = r2, Integrating by purts lI"ilh 11 = In x and rlv "" x, we finally Obillin
we have (rel)i:teing the are:l dement dx <ly by r (/1' I/O)
In x ! = x !n x - x + I.
/2 =
1,"1"
o 0
-0"
e
11"
rdrdO = ?_ 1"
0
e
-0,'rdr = ,-T .
a The I can be neglected when compured with x, und Eq. (A.3G) results.

 Appm diz A ppendix

1'1. Lagrnnfl'!'" V nde t f!rnllnf!tl J"ultlplie r "
This is a method whic h serves to find the critical points of a function of several
variables P(Xl> X2,"" 7 when the variables arc not independent, but nrc con-
ft )
strained by certain relations. SUPI>OSC, for example, that the constmints are
expre!ll>Cd by 411(xl> X2,"" :r~) = 0 and 412(zl, Z2, " " ZR) = O. T hen we only
have I~ - 2 independent variables. The eritielll pointll of F(ZI' X2, ,x,,) are
those values of XI, :1:2, , z" for which dP = 0 for sllmll changes il\ the variables.
Bllt
docs not im ply that dF/dz, = 0 because the changes dxl> dJ: 2 , . , dz" nrc not
independent. Ruthe r they are restricted by t he conditions
iJXI
x, +"
d 41 . = - , d - dX2
aX2
+ , .. +
- , d.x" =
ax!,
0 (A.38)
(A.3')
Let us now multiply Eqs. (A .38) and (A.39) by 1.11'0 arbitrary qua ntities or alld (j
and ndd them to Eq. (A.37). T he result is
Since we !lOW have II + 2 variables with or and (j arbitrnry, this implies that
i = 1, 2, ... ,11. (A .40)
T his set of 1/ equations allows us to obtain Xl, X2, ... , x" for a critical point of F
as a function of or lind {J. Substitution in 411 = 0 nnd 411 = 0 thell gives or and {J,
and hence we can compute Xl> X2, ,X R . This was the method used in E xamples
10. 1, 13.1, and 13.4 for obtaining the most probable partition of a system of parti-
cles subject to the requirements (constraints) of conservfltion of particles nnd con-
scrvntion of energy.
. -'1. Thf 1i.tt!Ction of Iartidell
T he 1I11:llysis of processes involving fundamental particles or nuclei requires tech-
niques which not only reveal the pagllage of It particle through a certain region but
in addition allow us to obt:lin informMion about some kinematical properties. We
nced to kllow the time of 1)3SS..'Ige, the direction of mot ion, the velocity, the momen-
tum or the energy, and some intrinsic properties such lIS the charge, the llIl1SS, or
the direction of the spin of the 1)(Lrlicle. No single detf!Ction me thod is capable of
giving inform:\lion about nllthesc qunntilies. In general , n combination of delf!Ct-
ing devices i ~ used for obtnining the infornlfltiun required in 1\ given cxperiment.
The detccting techniques depend on the effects produced by fL chllrged pMticle
whell it moves through n substance. When a ch:lrgcd pnrticle passes through
mlltter, it. c:m:<cs cxcitation :\lId ionization of the molccules of the m:llcri:ll. T his
iOlli1.ation i" the property on which 1lcarly all the in~t l'umcnt~ used for the detec-
tion of such particle8 nrc bu.scd. Similar instrument.':! can be used for ullcllargcd
rndintions (e.g., x-d.ys lind neutrons) because, by me:UlS of collisions, they give
ellerlty 1(1 chUflr;cd particles, which then cause ioni.z:ltioll. T he diITerent types of
i1lstl'ul1Ielltll diITer with respect. to the mat,erin! in which the ioni1.atioll is produc,ed
and the way it is observM or measured.
:\Iany inslmments al'(! based on the I)roduetion of iOllization in :l gas. It is
neee,>;slIry to >!C1),'1r:lte and collect thc positive lind negntive ions formed bccnusc,
if the.\' remained clu~e together, they would reconlbine in a vcry shurt time alld no
eleclrielll eITect which would re\'elll thc presencc of the particle could be obt{\ined.
1'111.' scpar:lti1m and collection of the ions rt.' (luires UII electric field, and different
im;[ rUlllen[ ~ result, depending on Ilhether the field is :;lIlall, large, or intermediate.
ill Ilmgllitude. The iOllizlItioll !lilly !ll~u be proUllcl,.'(! ill 'I liquid or in II solid. Whell
it is produced in :1 g'I.'1 IiUper5.:11Uf!IU.'<i with vapor, in a sllperhelltcd li<IUid , or ill
II phl)togml)hic emulsion, the. tracks of the pUrliclcs cnn be made \I~ible.
When pnrtieles strike certain liquid or solid materials eu!led fllI08/J/lOrlf, which
Imve the property of lutllille;;ccnce, part IIf the energy w;ed ill nlOlecul:1T excit!ltion
lind ioniz:uion is ~l\IittcJ :IS vi~ible or ultra\'illlet light. Sometimes thi.'l light
can be ob:icrved visuillly, or it mlly havc to be detl,.'Cted by more !i(:llsitive devices.
We ~hll il eOll~idcr .'!Ollie of the commonly USi..'(1 dell'ctioll methods, :llthough a
detailed t['{'nllllcnt is beyond the ;;C0I)C of this book.
A. TII/~ Scill /.ill(ltioll m e t lwd. It was found, about WOO, thM or-particlC!l pro-
duce 11lIllinl'~c(> lIce in zinc ,;ulfide, barium plntiuo-cY:lllide, tlud diamond. Thili
luminCSCCllCC conJ'ists uf :I large /lU/llber of imlividual flashes, which can be seen
through a llllIgnifying gl:l.o;s. Careful expcrimcllts h:\\'e I!hown that each or-I)''lrticle
pruduccs one ::;cintill:llion, so th!lt the number of u-Illirticles which f:III on a detect-
ing ~c rl,.'Cl\ i,; gil'ell dircctly by [he uUIll I)Cr of $Cinti llatioll~ counted. Thc counting
C:UJ be dOllc by lIIe:UlS of :I microscope with a lIl11gnificatioll of about 30, nnd
good preci.~ioll can be obtained, but with dilliculty. This method is esl)CCially use-
ful for counting cr-p',1rticles in the presence of other r:\dialions, bcc:IUse the zinc
liulfide scrccn is eompartllively inS()n~itivc to fJ- and 1'-l'ap. T he method wm; uscd
by Buthel'ford in 1910 to analyze the scattering of or-Illlrtieles by nuclei in thin
foils.
The u:;e of $;ciutillntion counters h:1S been v:\slly improved due to the diiiCOvery
of nell' lumincscent sub8t:lnces which arc aloo sensitive to {J- lind 1'-l'ays, ilud the
development of highly efficient photomultiplier tube" to detect the luminescence.
The nell' lIIalerilils include: inorganic w.lis, primarily the :tlkali halides, containing
SlIl:\][ amoulll!! of impurities as aelivntors for luminescence (for exnmple, sodium
or potMSium iodi{le aeth':tled with thallium) ; crys/al/iTle orgallie materials, such lIS
 566 A ppendi;r Appendix 567

+"",V +400V +600V +800 V + 1000\' from the cathode. Each particle incident on the phosphor produces a pulse, and
the pulses arc fed to an electronic system, in which they arc counted. Electronic
systems have also been developed which measure the energy of the incident par-
ticles; the resulting instrument is called a sci11lillation spectrometer. A schematic
diagram of a scintillation detector is shown in Fig. A- tO.

I' 8 , lotli.:;atio,~ i ll s l r umell t s: iotlizo(lliou c h a mbe r, p roport io nal counter ,

a'id Ceiger-Miille r coullte r . The I>rillciple behind each of these detectors is
l)ynOO~
the production of ionization in a gas and the scparntion and collection of the ions
by means of an electric field. The difTerences in the three systems can be explained
I-"ig. A- 9. Photo multiplier tube (schematic). with thc aid of Fig. A-I I, which shows a cylindrical conducting chamber contain-
ing a. central conducting clectrode located 011 the axis of the chamber and insulated
naphthalene, anthracene, and stilbene; and solutio/IS oj organic compounds such as from it. T he chamber is filled with a gas :1.t a pressure of one atmosphere or less.
tcrphcnyi dissolved in xylene. The photomultiplier tube, which replaces the micro- A voltage V is maintained betwcen the wall and the eentral electrode through the
scope and observer, converts the scintillations from the phosphor illto amplified resistance R. The central electrode is at a positive potential relative to that of the
electrical pulses which can be counted or otherwise analyzed with suitable elec- chamber wall.
t ronic equipment. The modern scint.iIlation counter call detect and record many
milllons of flashes ]>er second nnd can be used with intense radiations. l oni~inR I'nrlidc
A schematic diagram of a I>hotomuitiplicr tube is shown in Fig. A- n. Light .\nodc
from the lumin~ n t substance strikes the cathode (which is usually made of /
antimony and cesium) Ilnd ejects electrons by means of the photoelectric effect. Amplifier
/
T he tube has several clectrodes, called dynodes, to which I>rogressively higher lind
plIlIII! oollnter
potentials nre applied. The photoelectrons nrc accelerated by the electric field Clll hQo;\e/
/

-==- 1' Ii
between the cathode and the first dynode, which is at a positive potential relative
to that of the cathode, and strike the dynode. The accelerated electrons impart
enough energy to electrons in the dynode to eject SOllie of them. There may be
+
(II)
as many ns ten secondary electrons for each electron which strikes the dynode.
These secondary electrons are directed by the electric field toward the second dy-
node. This process is repeated and the electron current is amplified as the elec- \. " .I
trons arc accelerated from dynode to dynode. The output curren t, or pulse, at the I
anode may be morc than a million times as grent as the current originally emitted
I',,
I.ight ""fle.. tor ,
,
I gl t 1"1>e
.
<

I r-'" 1 \. , ,,,
\'

rh oton,ulti]llicr I 12)
, lul~
- Eleelronie
wUnlin!! syste",

1'1~l'llOr
")
,.
11'lI:h.\oIl"~
.1 Ii C
I'
(b)
D
"
1'''''.1'1" ""I'I,ly
Fig. A-II. (a) GlLS+filled CO UlItl?:r with l\S!IOCiated circuit (schematic). (b) Number of
ion pairs collected at the center electrode ve\'!!us yoltage for two events Icunes ( I) and
Fig. A-IO. Scintillation detector (schematic). (2)J with greatly different numbers of primary ion [Jllirs produced.
568 AppmJiJ;
Suppo'Sc that iOlliz;ltion occurs in the g[l.'l due to the passage of a charged parti.
cleo Each ion pair consists of a positive ion and an electron. For:l given init,ial
ionization, the number of ion pairs collected is a function of the applied voltage.
In Fig. A- II (b) curves (I) and (2) of total ion collection arc plotted:\8 functions of
applied voltage for t\\"o different kinds of ionizing radiations, sllch ;1S an alpha and
:\ beta particle or two bela particles of different cnergicl;. For convenience, the
logarithm of the number of ion pairs n has been used as the ordinutc. If there is
no voltage across the electrodes, the ions will recombine, and no pulse will appear
on the counter. As lhc voltage is incrcuscd, say to:\ few volts, there is competition
betwccn the IOi:;s of ion pairs by recombination and the removal of ions by collec-
tion at thc elcet rode~ :Itld some cleetrom; will reach t he centra.l elcctrode. At n.
voltage V 1 (of perhaps 10 volts) the loss of ions by recombination is negligible,
and all electrons I)roduced reneh the central electrode. As V is increased, 11 stays
constant until :\ voltage V 2 is reached; this voltage may be some tellS or hundreds
of volts, depending 011 the conditions of the experiment. The region B between
V 1 and V 2, in which the number of ion pairs collected is independent of the ap-
plied voltage and in which the curve is horizontal, is called the iOllizalior! chamber
regiot! .
When the volt age is incrcased above V 2, 11 increases becausc of a phenomenon
cHllcd gas lIlulliplicatiol! or gas amiJlification . The electrons rcle!\SCd in the primary
ionization lIequire enough enel"g.Y before they reach the anode to produce additional
ionization when t hey collide with gas molecules, and IZ increases almost, exponen-
tially with V. Each initial electron produecs a small ~nvalnnche" of electrons;
most of these secondary elcetrons are liberated close to the central elcctrQ([c.
The behavior of the t\\"o curves above I' 2, corresponding to different init i:ll ioniza-
tions, is intcresting. For some runge of voltages, UI) to 1'3, each electron acts
independently and gives its own avalanche, not being nffecled by the prelience of
the other electrons. Hence curves (1) and (2) continue parallel, with a constant
ratio of /!. Between 1'2 and l'a, or region C, the number of ion pains collected is
then proportional to the initinl ionization. This is the region of l)rOpOrliollol
counler oiJualioli.
Above 1'3, the gn.':HlIultiplic:\tion eITect continues to increase very mpidly lind,
115 more elect rons produce avalanches, the latter begin to interact with one nnother;
the positive-ioll space eh!lrge of one avalanche inhibits t.he devclopment of the
next avalnnehe. The dischargc with more initi:ll electrons (curve 2) is affected
before the one with fewer initial electrons (cu rve 1) and increases less rapidly than
the latter; cur ves (I) nnd (2) appronch each othcl" and cventunlly meet at an
npplied voltngc 1'". The region D between 1'3 and V" is the region of limited
proporliolWlity. A bo\"e I' of the charge collected becomes independent of the ioniza-
tion initillting it, and curves (I) and (2) become identical. The gas Inultipliclltion
increases the lotal number of ions to n vnlue thllt is limited by the characteristics
of the chamber and the external circuit. T he region E llbove IT" is !lIe region of
Geiyu-Milller coullier o'[leralioll. It end!! at a voltage V 5, where the discharge
tends to prOp!igate it self indefinitely; V 5 marks the end of the uscful volhlge scnle,
a
t he region'" above being that of continuous discharge. As result of the behavior
Appendi;,; 569
of the ions of the gas in the electric field of the counter, three detection instruments
have been developed.
I. Th e ionizatioll cliamber, which operates at voltages in the region B, is ehllrac-
te!"ized by complete collection of nil the electrons initially liberated by the passage
of the particle without gas amplification. Subject to certain conditions, it wi!! give
11 pulse prop01'liollal in magnitude to the number of thesc electrons. I t is used to
mensure the intensity of !11l ionizing radiation by measuring the mte of ionizntion.
2. Tlie 1)1oliorliollal COUlller, which operates in the voltage region C, is charac-
terized by a gas llIuitiplic:ition independent of the number of initial electrons.
Hence, although gns multiplication is utilizcd, the pulsc is always prOI)(lrtional to
the initial ionization. The usc of t his counter permits bot h the counting of single
evcllts and the determination of ~he energy of particles which do not produce
enough ions to yicld a detec table pulse in region B. The proportional counter,
therefore, oITers advantages for pulse-type 1l1easurelllcnts of beta radiation, an
a pplication for which ionization chambers are 1IO\' sufficiently sensiti ve.
3. Th e Geiyer-iI!ulla cowller, also known as the Geiger or G-M COUll Ie)", which
operates in t he voltage region E, is characterized by the sprend of the discharge
throughout the entire length of the counter, resulting in a pulse size iudependent
of the initial ionizntion. It is especially useful for the counting of lightly ionizing
pnrticles such as .a-particles oz l'-rays. The G-i\J counter usually consists of a
fine wire (e.g., tungsten) mounted along the axis of :\ tube which con tains a gas at
a pressure of about 2 to 10 cm of me rcury . T he counter may be a tube made of a
met!!l such as copper, or a metal cylinder supported inside a glass tube; a mixture
of 00% argon nnd 10% ethyl alcohol is suitable for the gas. A potential differcnce
(which may be between 800 and 1200 V) is applied to make the tube negative
\\"i~h respect to the wi re.
I n the Gciger-:'I[ulJer region a continuous discharge i~ produced by the release
of secondary electrons from the walls of the tube due to side effects triggered by
the initial avalanche of ions. These secondary electrons rcsult bccnuse, when a
positive argon ion, for instance, is neutralized on the metallic surface of the enth-
ode, a considerable amount of energy is relcased which may be used to expelll.n
electron from the cathode surface. These electrons, ill 1lI0Villg toward the ccntral
electrode, produce new ionizations, thus perpetuating the discharge. To prepare
the counter for a new event it is necessary to stop or "quench n the discharge. T his
quenching Illay be aceomplishcd by electronica!ly lowering the voltage I' after
each count. However, the quenching is usually done in the gas itself. If, for ex-
a mple, the gas is nrgon with 10% ethyl alcohol, t hen because of charge exchanges
in col!isions of argon ions with alcohol molecules, the positive ions reaching the
cathode are alcohol ions, and they do lIot, in general, release electrons from the
cathode surface ; the energy is uscd instend to break the alcohol molecule and the
discharge quickly stops after the initial avalanche reaches the elec~rodes. Second-
ary electrons are also rcler..scd by photons produced in the avalanche. The alcohol
molecules absorb the photons without releasing electrons.
570 Appmdiz
In the electric!\1 instruments discussed, the ions, either multiplied in number or
not, are collect.ed and produce ll. voltage pulse which may be as srll!\ll as 10 !AV. An
elcctronic pulse amplifier accepts these small voltages and IUnplifies them to II level
usually iii the range of ,) to 50 V. The amplified voltage pulses must then be
counted in some way .so th:lt their fatc can be measured. The number of pulses
indic:IIcd on the counter gives the number of pll.rticies that have entC!red the spnce
betwccn the electrodes. Other clcctronic dcviCCl! arc also available for measuring
the mngllitude of the pulse which gives the energy of the incident particle. Thus
one often wants not only to record t he occurrence of a pulse, but also to sort pulses
according to their size (by means of nIL electronic discriminator circuit) or to sort
thclll according to the time intervals during which they arrivc (by means of an
electronic timing circuit). The detector then forms part of a circuit with appro-
priate electronic instrUlllenlation.
C. Ne utron de fect ioll . :\Iost proecsscs involved in stopping neutrons in mat-
ter may be used for detecting neutrons, since charged ]>articles are set into motion,
either as a primary elTect or as a secondary effect after the emission of a gamma
ray. The processes utilized in neutron detection are;
(I) neutron-induced nuclear reactions yielding charged p:lrticle reaction prod-
ucts (prot<)Ils, o.l ]>ha particles, etc.),
(2) induced fission in certain heavy elements,
(3) clastic collisions hetwe<:n neutrons and lIuclei, notably hydrogen nuclei,
which arc thereby set into 1Il0tion,
(") capture of neutrons by certain stable isotopes, which arc thereby converted
into r:tdioisotopes emitting fJ- and "I-rays (activation method).
The classical example of neutron detection is the boron counter for slow neutrons.
This is a gus counter in which the inside wall is lined with boron or the counter
is filled "'ith BF3 gas, I>referably enriched in lOB. The responsible reaction is
IOB(n,a)7Li. The al pha particle and the tLi rccoiJnucleus both have short ranges,
so that in mos t of the events they collle to rest in the gas with all the relensed
cnergy converted into ionization and atomic exci ta tions. The counter is oper
ated in the proportionality region, and it is thus reasonably easy to discriminate
between the neutron-induced events and those due to gamma-ray or cosmic-ray
background. Other e;'am l)les of reactions that have been used for slow-neutron'
dete<:tors arc GLi(n,t)4 He, HX(n,p) 1 4 C, and 113Cd(n,"I)LL4Cd.
Nuclear reactions h:we also been utilized in fast-neutron detectors; however,
the efficiency ill not so high as in the boron counters for slow neutrons, since no
fast-neutron cross !;Cction comes anywhere close to Ihe magnitude of the lOB
cross section for slow neutrons. Since the BF3 counter is sueh an efficient and
simple counter for slow neutron$, one natural way of making a detector for fasl.
neutrons is to surround a BF3 counter with p<'lTflffin in whieh the fust neutrons slow
down by clastic collisions so that tht'y can diffuse into the counter as thermal
neutrons. The complete fnst-neutron counter can be made inscnsitive to slow
neutrons by cadmium shielding.
Appefldir. [j7J
,t'
o
,
--.-3
'.'
.1"
Fig. A-I2. Light ,,"ave front in Cerenkov radial ion.
D . Tile Ce,.etll;ov COIlIlI.er . The velocity of light in a trnnsparcnt solid or
liquid ill given by v = ell!, where n is the index of refrnction. If fI ehnrged particle
moving through this medium has a velocity greater than v (that is, greater than
tile velocity of light in tho medium), light is emitted by the atoms that are momen-
tarily electrically polarized by the chnrgcd pmt icle p:\.'SSing nearby. The process is
one in which the perturbation of the electric field on the atom produees :l. transient
dipole moment, which then causes emission of e1e<:tromagnetic waves. The reason
why such light is emitted only when the yelocity exceeds u = el l! is that only in
this CMe can light. from all atoms nlong the tr3ck be coherent. Figure A-12 shows
how a wave fron~ clin be constructed from elementary II'~LveS emitted from v!Lrious
points along the l>ath of the particle. For a given vclocity v.. of the ]>article, the
light is emitted in a cone, with the angle a given by sin a = IJ/u. = clrw,. A
siz~Lble fraction of the Cerellkov radiation is given ulT in the visible part of the
spectrum, wh ich also corresponds approximately to tho region of highest !;Cnsi-
tivity of photomultiplier tubes. Various types of CA!renkov detectors have been
built, in which only the light emitted in a IXlTticular dire<:tion is recorded. The
detector then is lL velocity-sensitive device. Obviousl,Y it can be used ollly for par-
ticles with v. > C/ I1.
E . T i, e cloud cltumber. One of the most important. instruments for basic re-
search on radiation is the cloud chamber. This instrument, first used in 1012, is
based on the discovery by C. T. R. Wilson that ions act as nuclei for the con-
densntion of supersaturated water vapor. In a cloud chamber, the gas, saturnted
with VI\])or, is mnde to eXlxmd by the quick 1IL0tion of a piston. The expansion is
adiabatic and lowers the temperature. T he cooling is llIore t.lmn s uffieienL to over-
come the effe<:t of the increase in volume, and the air becomes supcrstl.turated with
572 A,pptndiz
water va]>or. I f an iOllizing ray enters the chamber, the iOlls formed act as con-
densatioll poiJlt.'J for the vapor, alld the path of thc ray appears as a thin track of
fog. Tn most c)[pansion chambers, the gas- vapor mi.xture is air with waler, or
argon with ethyl alcohol, at atmospheric pressure.
A simplified diagram which indicates the principle of t.he cloud chamber is
shown in Fig. A- 13. A cylinder C is closed at. one end by a glass window IV lind
at the other end by a metal piston. A small amount of water in the chamber
kccps the air saturated. When the piston is pulled dow n, the air becomes super-
saturaled as described above and, in the presence of ionizing radiation, fog tracks
are formed. The t racks can be illuminated by light from t he side and viewed or
photographed through the window. The iOlls can then be removed by means of
an electric field betwccn the piston and the metal ring. The piston is retumed to
its original position alld the chamber is rcady for another burst of radiation.
Fig. A-1 3. Wilson cloud cha!\\oor
(schematic).
T he Wilson cloud chamber makes it possible to study the interactions that take
place betwccn charged particles and individual atoms by photographing the
actual paths of ionizing radintions, which may the n be analyzed at leisure. l\'lany
modifications of the original cloud chamber have been made. For example, in
order to obtain large numbers of photographs, arrangement.'J have been made so
that the expansion can be rel>co.ted automatieal!y and photographs taken con-
tinuously. If two stereoscopic pictures arc tuken simultaneously, lhe path of the
particle in space cun be rcconstructed.
When 0. cloud chamber is placed betwecn the pole pieces of an electromagnet it
is poesible to distinguish between IXlSilively and negatively charged particles.
From the curvature of the path of a particle in the magnetic field, the sign of the
charge and the magnitude of the momentum of the particle can be determined.
Different p:lrticles produce diffeTCnt types of tracks. Thus heavy, slow particles
such as a-particles produce broad, denscly packed tracks with occasional sharp,
small-angle bends, especially ncar the end of the track, due to a sudden deviation
resulting from a collision. Slow clectrons produce narrow, beaded, tortuous tracks,
since they unde rgo many scat.terings, while f(lSt particles, both light and heavy,
produce nnrrow, beaded tracks.
F. r ile bllbble clwrnbe r . leor high-energy particles, one disadvantage of the
cloud chamber is that the density of the gas is not great enough to cause an ap-
preciable number of interactions to take plo.ce in the chamber. More important
perhaps is that thc cloud chamber has a very long recovery time (of the order of
5i3
tens of seconds) after each e)[pansiol!. In elemcntary-particle research, therefore,
the cloud chamber has been all buL repJnecd by the bubble chamber, which is, one
might. fS.: !y, :Ul inverse cloud chamber. A bubble chamber contain~ a ii<luid at a
pressure :lnd temperature such that it is just below its boiling [>oint. If the pressure
is suddenly decreased the liquid beCOI!!CS !Superhellted aud bubbles start. to develop,
prefe rentially forming nround ions. In the hydrogen bubble chamber, !Super-
heated liquid hydrogen (.... 200 ] { ) is the medium through which the particles pas.';.
T he ions left in the path of il charged l)article become cval>Or:tlion nuclei for the
liquid hydrogen, and the trail can be 8C('n and photographed as a chuin of bubbles.
Whcll particles which interact strongly with protons pass through the bubble
chamber, reactions take place, and the trails of the incoming pflrliele, as well as
the reliction products, can be swdiccJ.. If the bubble chamber is I)laced in :~ mag-
netic field and photographs arc taken , the charge and the momentum of the
various p:lrUcles can be measured in the photographs.
G. 'fIr c '~/H.r k clJamber. One of the nel\'e~ L inventions in the nrc:!. of high-
cnergy detectors is the spnrk chnmber, which consists of It number of met,lIllic
plates insui:lted from e:!.eh other find with a uniform neon-filled gap of thc order of
n few millimeters betwccn them. Every other plate is grounded, and the intcr-
leafing pllltes lire given a short voltllge pulse (O.5 ps) of such a mugnitude that
!Sparks will occur at places at which the gas is ionized. The trail of ions left. by a
penetrating particle will trigger such sparks; a photograph of the sparks betwccn
nil the piates gives all outline of the path of the particle.
11. I>/, olographi c e mulsiotls . An ionizing particle traveling through the emul-
sion of a [)hotographic plate leaves a track containing a number of sensitized silver
bromide grains. Specifll photographic emulsions, cnlled nucle'lr emulsions, have
been developed. They arc distinguished from optical emulsions by their high sil-
ver bromide content (which may be as milch as four times !IS great ItS in photo-
gruphie [)lntes), by gr:!.in ;;i1.e, and by the thickness of the emulsion. Like the
cloud chamber, the photographic plate, when it has been developed, reco rds the
path of the particle, and a variety of information can be obtained from the study
of the tr.lcks. Counting lhe individual paths gives a measure of the number of
particles entering the plate, and detailed study of the tracks yields information
about the mass, charge, and energy of thc particles. The photographic ellluision
offers adVlUlt:lges over the cloud chamber in that the emulsion is solid, so that the
tracks nrc short, and its sensitivity is permanent rather than restricted to infre-
quently repeated short intervals. On the other hand, to record specific events, the
difTeren~ chambers can be controlled by means of coincidence circuits, a process
which il! not possible with photographic emulsions.


TABLES

."

ANSWERS TO
ODD -NUMBERED PROBLEMS

INDEX
 Tobie A-3 Units a nd Symbols
Quantit y Sy m bol Na m ~ or un it Re latio n to r un d a n n, nta l un it.
MKSC MKSA
Tubit . 577
Length I, meter m
M~ m kilogram kg N ATUR AL TH I GONO;\I ETHIC FUNCI' I ONS
Time eeeond
m ol- I
Velocity m ,-a Angle Angle
Acceleration o D~ R.- e~ Tan- 0.- Ra- e~ Tan-
,-' S;nc g<,nt

.
I Angular velocity g= dian Sine sine g<, nt g= dilln sine
Angular frequeney ,-' 0- .000 1.000 0.000
Frequeney herts ( Hs) ,-' I' .0 17
0.000
.018 1.000 .018 ' 0.803 0.719 0.695 1.036
~Momentum p m kg ,- I 2' .035 .035 0.9'J9 .OJ' 47 $ 20 .731 .682 1.072
Fo= p newton (N ) m kg ,-2 3' .052 .052 .m .052 48' .838 .743 .669 1.11\
.998 .070 49' .855 .755 .656 1.150
Angular momentum J, m2 kg ,-I " .070
.087
.070
.996 .088 SO' $73 .766 .6-13 1.192
Torque ,
\I' joule (J)
m2
m2
kg , -2
kg ,-J
"
0'
7'
.105
.122
.087
.105
.122
.995
.993
.105
.123
51'
52"
.890
.908
.777
.788
.629
.616
1.235
1.280
Wo rk
1.327
Po",er
Energy
P
r:,. E" U, E
watt (W)
joule (J)
m2
m2
kg s- 3
kg ,-2
8'
9'
10'
.140
.157
.175
.139
.156
.174
.990
.988
.985
.141
.158
.]76
'"
54
55
.925
.912
.960
.799
.809
.8UI
.602
.588
.574
1.376
1.428
.Temperature T 'K m 2 kg s- 2j particlc II' .192 .19 1 .982 .194 56' .977 .829 .559 1.483
Coefficient of diffusion D m2 a- L 12' .209 .208 .978 .213 57 .995 .839 .545 1.540
)3' .227 .225 .971 .231 '8' 1.0]2 .848 .530 1.600
Coefficient of the rmal 1;' - .2H .242 .970 .24D 59' 1.Q;l0 .857 .515 1.664
K m kg a- 3 - K - I .966 .268 60' 1.017 .866 .500 1.732
, conductivity
Coefficient of vi~osity
You ng's modulus
,
I'
m-I kgs- L
m-I kg ,-2
'"
16'
17'
.262
.279
.297
.259
.276
.292
.96 1
.956
.287
.306
61'
62'
I.OOS
1.082
.875
.883
.485
.470
1.804
1.881
)8' .3 14 .309 .951 .325 63' 1.100 .891 .'154 1.963
m- I kg s- 2
Bulk modulus m- L kg a- 2
19'
20-
.332
.349
.326
.342
.946
.940
.344
.364
MO
65'
1.117
1.13.(
.899
.906
.438
.423
2.050
2. 145
Shear modulus G
Moment of inertia
Gravitational field
J
S
m 2 kg
m ,-2
21'
22'
.367
.384
.358
.375
.934
.927
.384
.4114 ,,'68'
W' 1.152
1.169
.91 4
.921
.921
.407
.391
2.246
2.356

G ravitational potential
'Charge
V,
.,Q coulomb e
m 2 ,-2
A,
,.'
23'
25
.401
.'1]9
.436
.391
.407
.423
.921
.914
.906
.425
.445
.466
69'
70
1.187
1.2<14
1.222
.934
.1140
.375
.358
.342
2.475
2.005
2.747
J ampere B- 1 C A 26' .'154 .438 $99 .488 71 " 1.239 .9~6 .326 2.904
Eleelrie currtnt 27 $ 91 .5 10 72' 1.257 .95 1 .309 3.078
mkg s-' A- L .471 .454
G III kg s-'C- I
Eleet.ric field
Electric potential V volt (V) m 2 kg ,-~ C-I
m- 2 ,-I C
m2 kg a- J A- I

m- 2 A
,.'
28'
30'
.489
.506
.524
.470
.485
.500
.883
.875
.866
.532
.55<
.577
73
74'
75'
1.274
].292
1.309
.956

....
.96 1
.292
.276
.259
3.271
3.'187
3.732
Current density j
.242 4.0] I
Electrie resistance
Inductance

L
ohm (0)
hen ry (H )
m 2 kg S-I C-~
m 2 kg C- 2
m2 kg s-3 A- I
m2 kg a- 2 A- I
3/'
32'
33'
.541
.559
.576
.515
.530
.54'
.857
$48
.839
.601
.625
.649
70'
ii-
78'
1.326
1.344
1.361
.970
.974
.978
.22'
.208
4.331
UM
Electric permittivity
Polarization
'0
@
m-l kg-I S2 C2
m- 2 C
m - 3 kg - l s A'
m- 2 , A ,,'
34'

36'
.593
.611
.628
.559
.574
.588
.829
.8 19
.809
.675
.700
.727
79"
80'
81'
1.379
1.390
1.414
.982
.985
.988
.191
.174
.156
5.145
5.671
6.314
m- 2 C m- 2 A .602 .799 .754 82' 1.431 .990 .139 7.115
Dielec tric displacement
" lesla (T) kg s-I C-I kg a- 2 A-I
37
38'
.646
.663 .616 .788 .781 83' 1.4<1 9 .993 . 22 8.144
lI.Iagne tic field
Magnetic pe rmeability " m.kgC-2
m-I ,-I C
mkga - 2 A- 2
m- I A
39'
40'
.681
.698
.629
.... 3
.7ii
.766
.810
.839
g.,"
8"
1.400
1.484
.995
.996
.105
.087
9.514
11.43
M agnetization
Magnetizi ng field
Magnetic fl ux weber (Wb)
m- I S-L C
m 2 kg S-1 C - L
m- L A
m 2 kgs - 2 A- 1
,,'
4]

43'
.716
.733
.751
.658
.609
.682
.755
.743
.731
.869
.900
.933
80'
87'
88'
1.501
\.5]8
\.536
.998
.999
.999
.070
.052
.035
14.30
ID.08
28.64
SO' .018 57.29
Electric dipole moment
Electric q\ladrupoJe moment
me
m'e
m.A
m 2 ,A
,,'
4" " .708
.785
.695
.707
.719
.707
.966
1.000 90'
1.553
1.571
1.000
1.000 .000 00

Magnetic dipole moment m 2 S-I C m'A

Magnetic quadrupole moment m 3 11- 1 C m' A
Capacity farad (F) m-2 kg-L s2 C3 m- a kg - L, 4 At
1__ ~ _ _ _ _ _ _L -__~~____~____~L-____' ~
578 Tabltl 579

CQ)IMON LOGARITHM S
CQ;\IMON LOGARITIIMS (conjin~

,
,, ,=
. ....
.,,' .
.-...
dH
~"
"'" ''''
361~
"" H7'l

,
"'''
Hi!

.'" .,,'
"'
.m"
~ gl ~
"
"'". ..
""
72n ,m
"" M~ "" "
~,

""
...
"",
,,~ 6721

,8 M" ""
1182 "
"''' "" , HM
7993 "" '''' ,,"'
; ~ S2
~19~ 8325
"" "" ""
.,," "''' .,,' "" "" "" .,"
Mi3
Olgl
"'" "'" ""
"" "" "" DH5
8976

""

580 Tabhl

EXI'ON ENTIAL F UNCTIONS LIST OF TABLES

.. ,-. " ,-'

0 .00 1 .0000 1.0000 2.5 !2 . 182 0 .0821
0 .05
0.10
1 .0513
1. 1052
0 .9512
o 9\).18
2.6
2.7
13.464
14 .SSO
0 .OH3
0 .0672
0 . 15 1. 1618 0 .8001 2.8 160445 O.OOOS
0.2(1 1.2214 0 .8181 2.9 18 . 174 0 .0550
0 .25 1.2840 0 .7188 3.0 20 .086 0 .0498
0.30 1.3499 0 .7408 3. 1 22 . 198 0 .0450
0 .35 1.01191 0 .7047 3. 2 24 .533 0 .0408 TADLP. 2- 1- Energy level~ an d degenemeies in a cubical box 69
0 . 40 1.4918 06103 3 .3 Z7 113 0 .0369 TAIIL~ 2-2. Wa\'e funct ions of a h.srmonic OI!Cilla tor 72
0.45 1.5683 0 .6316 3.4 29 .964 0 .0334 Vibrationa l ene rgy levels for a,,;i:11 mot ion of N atom ill N 6 3 molecule
TAOLE 2- 3.
0 .50 I. 6487 0 .6065 3 .5 33 . 115 0.0302 relative to t he grou nd state 87
0 .55 1.1333 0 .5769 36 36 .598 0 .0273 TAOL~ 2- 4. Quantum operators 99
0 .60 I. 8221 0 .5488 3.7 40 . 441 0 .0247 T AB U : 3-1. Hydberg's constant 112
0 .65 1.9155 0 . 5220 3 .8 44 .101 0 .0224 T AO L E 3-2. Energy corrections when nuclcsr moti on is considered 115
0 .10 2.0138 0.4966 39 490402 0 .0202 T AlI L E 3-3. DCIlignation or angula r momentum states li nd essential degeneracy
for motion under centml forte3 118
0 .75 2. 1110 0 . 4124 4 0 54 .598 0.01 83 TAlI LE 3- 4. Angular fu nctions corresponding to L' and L. 123
0.80 2.2255 0 . 4493 4. 1 00 .310 0. 0166 T AIl/. r. 3-5. Angular functions corresl)ondin g to L2 and L; 123
0.85 2.3396 0 . 4274 42 6668a 0.0150 TAnLt; 3-6. Radial wave function of hydrogenliku atoms 125
0 .90 2. 4596 o 4066 4.3 13 .100 0 .0 136 TAOLE 3-7. Designation of electronic states 139
0 .95 2.5857 0 .3861 44 81. 451 0 .0123 TAULE 4- 1. Elec troni c configuration of atont3 162
1.0 2.1183 0 .3619 4.5 90 .011 TAB L E 4- 2. Terms of equivalent electrons 166
0.0111
1.1 3 .0042 0 .3329 4.6 99 . 484 0 .0101 TAULt: 4- 3. Possible III! nnd III. value~ for the lI p2 conligurntion 170
1.2 3 .320 1 0 . 3012 4.7 109 .95 0 .0091 TABLE 5-1. Electronic conliguration of homonuc!ellr dialomic molecule9 196
L3 3.6693 0 . 2725 4.8 121 .51 'rAUL' : 5-2. D i~u.li on (lIIerg)', bond lengths, and elect ric dipole moments of
0.0082
L4 4 .0552 0 . 2466 4. , 134.29 0.0014 some diatomic molecules 199
TABLE 5-3. Rotational and vibmti onal constanta of some diatomic molecules 213

1.,
1.5 4,4811
4 .9530
0 . 2231
0 . 2019

6
148 . 41
403 . 43
0 .0061
0 .0025
T AiILI: 6-- 1-
T AIlLE 6--2.
Fermi energy
Effective lUllS!!
24'
251
L7 5,4739 0 . 1821 7 1096.6 0 ._ T AULt! 6-3. Energy gal' S 265
18 6 .0496 0 . 1653 8 2981.0 0.0003 T AULE 7- \. Properties or some nuclide~ 291
I.'
2.0
6 .6859 0 . 1496 9 8103. 1 0.0001 TAJ:lLI:: 1-2.
TAB L ~: 8- 1.
Number of stable and very 10ng-liI'ed nuclides
The uranium !!Cries
315
33 1
1. 3891 0 . 1353 \0 22026 0 .00005
2. 1 8. 1662 0. 1225 TAULE 8- 2. Q-valuCll for emission of different nuclear particles from 232U 340
2.2 9 .0250 0.1108 'l'AfIU: 8- 3. Fissionability of heavy nuclei with the rmal ncutron~ 358
2.3 9 .9742 0.1003 T AUU; 8- 4. Threshold energies for photofission 358
2. 4 11.023 0 .0907 TAIIU: 8- 5. Propertics of somc fissionable materia ls for thermal neutrons 360
'rAUL!: 9 1. Fundament..'ll pa rticles 378
'rABL!; 9-2. l'nrticle decay modes 387
TAIH.E 9- 3. Isotopic spin, 8trangencSoI, and hypercharge of mesons and baryons <00
TABU: 10- 1. ValnCll of eri(;l:) 459
TAIlU: 12- 1. Van der Walll~ constants 503
581
 "'2 Li#1 0/ Tabit: ANSWERS TO ODD-N UMBERED PROBLEMS
TABLE 12- 2. Characlerilltic tempemlllres for rotation and \'ibrntion of diatomic
molecules 50S
T AUL,- 12-3. RatiO!! of the heat tal)acilicg for !lOme gases 514
T ABLE 13-1. Fermi energy and Fermi temperature of severnl metab 524
TABLE \ 3- 2. Values of the work fun Clion and the thermionic constant obtained
experimentally from Eq. ( 13.1 1) 527
T ABL!:: 13- 3. Debye temperatures of some solids 538
>

C IIAPTER I
1.1 (b) JOeV _ 1.6X 1O -1~ JJ 5X 1O~ tV _ 8.01 X 1O -I~ J , J MeV - 1.6X 1O- 13 J
(e) O.tXHc, O.29!lc, O.814c
1.3 1.78 X 103 J
1.7 (a)!X 10- 11 1' (b) 1.33X 1Q -6 W m- 2 (e) 4.22 X JO-u Jm - 3
(d) I.4XlO - 23 m - 2 kgs - 1; (el 167 W
1.9 "' (1') _ (8JrI!~3Ic3) e- A IU'; t(l') _ SJrkTI'2jc 3
1. 1141 00 o K ; O.21 4 J m - 3
1.1 3 (a) 1.70 X 10 10 elcctrone m - 2 S-I (b) 3.0 X 10 - 0 W m- 2; (e) 1.76 X 10- 19 J
1.1 5 (a ) 4.555 X 10 14 H z (b) I.SSeV (e) 4.]274 X IO - U Jl!C -1
1.1 7 (a.) 1.024 X 10- 10 In (b) 4.7 ] X 10- 17 J, 4'1.3- with respect to the incident
direction
1.19 166.8 keV _ 2.67 X 10- 14 J , 7.43 X 10- 12 m
1.23 (a) 5.03 X 10 11 Jlhotons m - 3 (b) 2080 photons m- 3
. 1.25 (a.) 1.24 X 10- 9 m (b) 1.24 X IO - CI m (e) 1.24 X 10- 4 m
l. 27 (a.) 4.892 eV (b) 6.7064 eV, 4.8922 eV, 3.9614 eV, 2.2723 eV, 2. 1465 eV
1.29 2.65 X lOa H ~, 1.13 X 10- 7 m
l.31 3. 1 X 10- 11 m
1.33 7.5 X 10- 3 eV in exce!lll or the binding energy
1.37 127
1.3!) 1.05 X 10- 4 m, 2.39 X 10- 3 m, 8.77 X 10- 3 m
1041 (11.) 8 (b) 40 (e) 100
1.43 i .98 em, 8.06 em
1.47 547'
1.49 (a) for the prolon: 3.9 111, for an electron: 7.3X 103 nl
(b) with unlimited precision for both eases
1.53 I.03X 109 1h or4.26X IO -Cl eV;5.15X 10 14 I1 z or 2.13 J\lcV
1.55 (a) !J.~ - ~4E~/.4

CIIA I'1'EIl 2
2.3 Energy difference between levels (11) increases (b) dceren.scs
2.5 3.8 X 103 :\[e V; Epav - 6.3, X 10- 17 eV, ~'... ul - 1.44 X 104 :'I IeV
5113
58" AIUU!U$ fa oM-numbm.d problmu A ~,., 10 odd-n~,.t:d pn1bltnu 585

2. 13(11.) (ma 2/211"f12) dR (b) (a 2p/2rh 2) dp

-laX +( I) "h.X+(2) IhaX+(3)
2. 15(0.) 8.27 X 10 - 13 eV (b) 2A8X 1O - I~eV (c) 1.34X 1O- 3 eV
I
2.2 122.7 MeV 4.3 "'10"2. - - 'haX- (I) "".L(2) - laX_(3)
2.23 (a) B _ I- A (a 2 + 1;2) sinh aa)/ R, C _ A (k 2 - iJw.)e--/ R,
Vii
-2aX+{I) ","2aX+(2) ","2aX+(3)
D - - A(k 2 + iJw.)e-/ R, A' - -2A(iJw.)e-... / R,
whcre R _ (a 2 - k 2) ~inh aa - 2iak cosh aa ",,".x+(1) "'aX+(2) -aX +(3)
(b) B _ - iA{k'2/k2 - I ) sin k'o./R', C _ - A {k'/.i:+ I)e- a'./R' I
D _ - A (It!/.i: - I)ea"/R', A' _ - 2A(It!/k)e- a ./R', 4.5 ",".,." - Va ","p(+ I)X+(1) ","p(+I)X+(2) ",,"p(-!-OX+(3)
where R' _ i(1t!2/P + I) sin k'a - 2(k'/k) COl! Jr!o. -p(O)L(I) "'p(0)L(2) ","p(0)L(3)
2.25 t: < b'o: "'. _ Ae- ;b -!- Bea " "'3 - Ce-'~ + De- ', "'2 - Re-
u

+ [o'e - ""',
"'I _ Ce - a ,;
,

4.7 See Table <I- I for vlJ,lue~.

150 < E < Eo: "'. and "' ~ as above, "'2 _ b'ea"z +
fo't-;k"" - I as above; <1.11 (a) 28 (b) 2p, 21), ~ 8 (c) 28,20 , 2p, 41' (d) 21' (e) 21',20,2)0' , 20,2 11 ,
E > Eo: "'~ as above, - 3 - Ct"'" + De-a'., -2 _ Ee"'''' + 1i'e -""~, "'I as above .8, .1>, ~F, ~O (r) IS, I I', ' I), 1)0', IG, 3S, 31', 3D, J)o', 3G
+
2.27 E < Eo: "'I _ At az Be-a., -2 - Ce- -!- De-', "'3 _ Ee;h + Fe- u " 4. 150,0,0;;,0, t;O, I, I; 1,1, 2; I, 3, <I; 2, 2, IjO, 2, 2;i, 3,t
-4 - Ce- ' + J1 e-,-$ - Ie""; <1. 19 Calcium: t; aluminum:!
[0; > Eo: "'I, "'3, and - 6 118 above, "'2 - Ct."'"+Dt.-;-', "'4 _ G,a'. +
He-a' . 4.21 6439 A and (6439 0.26) A
2.29 (11.) (_h 2/ 2m)d"l,jl/dr. 2 - f.:.r:t/I - E- (b) No 4.25 8.58 A
2.31 (d) - Eo+ lI (a b'o/2m)'12 4.27 Lithium: 28, - 5.315cV; 2p, - 3.54 eV; 3s, - 2.01 eV
2.39 )o'or d/d.:r.: (a) Yea, ik (b) Yes, a (c) No. For d 2/rh 2: (11.) Yell, _ 1;2 (b) Yell, a 2 Sodium: 3-'1, - 5.120 eV; 3p, - 3.028 eV; <Is, - 1.967 cV (3d at - 1.52 eV)
(e) Yell, _k 2 4.29 Aluminum: 1.9keV, 11 5eV;oxygen, l.l keV, <l6cV
2.4 1 For n - 0 : 0, h/2"IIN, 0, tmhw; for n - I : 0, f,.j6"IIN, 0, lfmhw 4.31 Aluminum: 8 AO A, 1470eV; 1)()l.a.'Isium: 3.59..\, 3452eV ; iron: 1.74 A, 7121 eV;
2.43 l . _ - ih(ya/az - ,a/ay); l .. _ -ill(z ajaz - za/ az); l , - - ill(% a/ay - ya/az) nickel: 1.55 A, 7965cV; l inc: 1.34 A, 9221 eV; molybdcnum: 0.664 A, 18,700eV ;
2.45 ..,III/2m"" O/- ivt"m"" 0 silvcr, 0.525 A, 23,600 eV
2.47 6n _ I, 3, 5, ... 4.33 (b) 8.3 keY, 1.495 A

CIIAPTER 3 CIIAPTEH 5
3. 1 '" - 4.134 X 101'/ n3 , - I; E .. _ - 4.36 X 1O- 18/n2 J ; 151 _ 2.18 X 1O - 18/n' J 5. 1 (a) - 16.25eV (b) 10.95eV (c) 15.43eV
3.3 (a) 8.22 X 10&orbi~ (b) 1.95 X 104 orbil.3 5.3 61.06 kcal mole-I
3.5 6AlI_1) - 1.78 A, 6A II_T - 2.38 A 5.7 (b) (., ~18)2(.,u I S)2(.,&2s)2(l1 u2sF (11 &21 2(... u2p)4 (...,2,,)4 (l1 u2p)2(11.&)2
3.9 (a) 6.58 X JOIS/ n3 liz (b) 6.58 X 10U(n - t)/{n(n - 1)2 liz (0-uJ,,)2(0-.3p) 2(... u3p) (...cJl2; 3X. -
3.17 l . _ - ihl-sin,piJ ja9 - (eotgeos,p)iJ/J<P); 5.9 (11.) Li+ H- (b) H +I -
l w - -ih[c08,p a/iJ9 - (cot (J sin~) iJ/J<Pl 5.11 5.45eV
3.29 2<10 5.138.37eV;6A5eV
3.33 615" - iA;M?d - !A, 1'\A;6E1 - iA, -hA, -:hA, 5.23 5.06 X 10- 30 m C; 0.33
where A _ 21E.1 Z2a 2/ n 5.25 17.7 A
3.35 Ye., (6A - 8.2 X 10- 11 m) 5.27 2.83 A
3.37 2.41 X 10- 21 N; 0.042 mm 3.39 2.8 X 101l 1h. 5.29 For H3~CI: (a) 21.5015 em - 1 (b) 2.6658 X 10- 3 eV, 7.9974 X 10-3 eV
(c) 6A50 X 10 11 I!z (4.65 1 X 10- i m), 12.000 X lOll lI z (2.326 X 10-4 m)
(d) 21.50 em- I
CIIA I'T~R " 5.3 1 (11.) Brol - [l(l + I) + t
m 2)h2/2 11, (b) Ero. - [/(1 + I) -I m 2)h 2/2 11
<1 .1 - 57.8eV, - M.geV, - 55.2eV; rolative to thc He+ ion (- 54AcV) these are 5.35 1.006 X 10-1 N m- I
- 3.4eV, - !.5eV, - O.SeV 5.37 5.162 X 102 N m- I; 0. 186 1 eV
 587
"6
8.2!l (a) Z7.98215amu (b) 23.98676aml.l (c) 27.98 192amu (d) z.I.9S5S6a.mu
CIlAPTER 6
8.31 (a) 1.535 ).leV (b) 2.34 MeV
6.1 3.686eV 8.33 A straight line
6.3 6.371 eV moleeule- I 8.35 (a) 1.74 X 1014 atolIl$ (b) 22 b
6.5 3 X IOL~ Ih 8.37 1.806X 10- 11 8.39 2.77 em
6.9 6.934 X 105 kga-'; 4.885 X 1O i5 ,-1,6.026X 1O!5~-1 8.4 1 188 MeV 8.43 1.2 X 10-' kg ,-I ; 2.6 yr
3
6.11 4.560 X 10'8 atoms m- 3 ; 8.498 X I O~8 aloms m- 3 ; 1.660 X 10'9 atoms m- 8.45 232Th : 4.95 MeV; 233Th: 6.11l\leV; 233U: 5.85l\1eV; 23tU: 5.26 :\ leV;
6. 133.151 eV; 4A45eV 2391>u: 6.45l\1eV; 240pU: 5.41 ;\leV
6. 17 m: _h/2a, and iJ2 z Jot' _ 2fadA~, where i stands fo r 2:.1/. t, respeeUvely.
8.47 7.28 MeVi 2.92 X IOu W
6.21 (a > n7:/2a (b) f,,' /(2{Ja' COS .1:0) 8.49 1.28 X 1011 yr
6.23 4.8 11 X 10-1: m 'If
6.25 Approximate ly 1 atom in lOe~ ~ j, .
6.27 3.63 X 10- 14..8; 1.39 X 10' m ,-I; J .98 X 107 m - I ; 5.05 X to- 8 m ClltlPTEn 9
6.29 lOa 6.33 1.057 X 1O-IOm3 C-I; 62.I G 6.35 L65micron~
9.1 (a) 3.7 (b) 5.26 X 103
9.3 (11.) 2.53 keY (b) 2.85 X 10- 13 m (e) 11~Ag
CIIAPTER .,. 9.5 I:eat mass: 502l\leV ; E k : 680 i\leV
9.7 7480 MeV
7.5 3.62X JO-u m ;6.00X W- 15 m;8.28X to - 15 m
9.9 'For Fig. 9-10: 1840 l\IeV; for Jo"ig. !HI: 18 10 i\leV
7 .7 28Si, 211Si, 30Si
9.15 Ca) 0.511 i\JeV (b) forward: 1.44 )'lcV, backward: 0.58 i\leV
7.130.85 MeV ; 0.76 MeV, yes
9.17 (11.) 8.3 GeV (b) 6S GeV
7.15 1Li : 39.24l\1eV, 5.61 MeV nucleon -I; 16(}: 127 .62 MeV, 7.98 MeV nucleon-I;
H Fe : 499.90 MeV, 8.77 MeV nucleon-L; 178Lu: 1417.97 l\I eV, 8.06 MeV nucleon-I 9. 19 1<l3.8l\1eV
9.21 (al :I ... I , :I" .. t, :I..... 0, 3K"! (b) 3 . .. I, :I .. .. !, 3.\ .. 0, J. - 0,
7.17 13(27 AI); 2$(84Ni); 36(82Kr) i 52(12~e); 72(ISOH)
cannot oeeur due to nonconservalion of 3, 3.. and S.
7.195.062 X 10- 3 amu
7.21 1.0078217 amu, 2.014100 amu, 15.99492 amu
9.23 (a) p+ + p+ --> p+ + A" + I{ +
,.,! ! ! 0 !
7.Xl 2.16 X 1O- 13 m " ! ! ! 0 !
7.29 3.62 X lOt partieies ,-I S: 0 0 0 - \
7.31 2.80 X 10- 1 $ m :I.. :I, and oS are conserved.
7.33 O.I50b 9.25 :1.. :1, and S are conserved ; 27 10 MeV
7.35 (a) 2U : ( 1'112)P(ilI/2).; 3n : {I'1{2).. (h~{2) .. ; 3Ue : ( la~12Ml sI12).; 9.33 t; remains invariant; <B goes to - al.
( 22122 4 24
He : ( 1' 112)..("112).; C: (hI12IP312, .. (1s112Ip3{2).. ;
i3 C : ( h~{2 I p~ 12M I ,b lpbl pI 12).. (b) 0 or 1;,;;; 0; 0;;
7.37 11 .. 50,222 keY; A .. 100,74 keY; A .. 150,38.2 keY CIlAPT1( 10

10.1 0.206; 1.014

10.3 3480 " I(
CIlAPTEI( 8 10.5 (b) U _ -p-u!:J,N tanh (,uIl<B/k T) (c) as T -+ 0, Z ..... 2 and .11 ~ -~~<B n/k T;
1
8.1 (a) 7.86 X 10-8,- 1 (b) 5.27 X lOll a-I; 112 yr (d) 1.32 X 104 8- as T ..... 00, Z --> 00 8nd!of --+ -~1l11.
8.9 28 mg 8.13 m" 10.9 U .. - 1'1l(J3g[(J +;) +
eoth (J ;):t - ! coth !x]
10.11 ( E' i/Ez)lne-(E, -B.111T (11.) 6.3 X 10- 9 (b) 0.395 (c) 2.M
8.17 Q/I+ .. 0.64 MeV; Q~- .. 0.565 MeV; Qc .. 1.66 ~ l eV
10.13 (a) 4.8X 103m ~-I, <I.4X 103 m a- 1,3.9X 103 m8 -1 (b) 2.25 X 103 1\1S-I,
8.19 18.63 keV
3.9 X 103 m 5- 1, 7.12 X 103 m 9- 1, 2.25 X lO i In 8- 1
8.23 (a) ~1Na (b) ~Xp (e) np (d) "I (e) ~H (0 (g) ~Cu (h) "I
I!tln 10.15 (a) 1.11 X 103 m 8- 1 (b) 5.16 X 103 m ,-, (c) 2.16 X 103 m 8- 1
8.27 UC(p, "I) 13N ; uC(d, "I) i4 N, uC(d, p)13 C , 12C (d, n/ 3N, 12C(d, o:)IOB; uC(o:, 1')1110
588 All6Wtrl fo odd-numbt,~d prob~frI$

10.17 (8) 0.166 (b) 0.163

INDEX
10.23 (8) 42% (b) 8% (e) 43.8% (d) 6.2%
\ 0.27 (a) 0% (b)35% (e) 93%
10.31 (b)). _ h/(Zm.l:T)"' - 1.8 1 X 10- 10 m

CIIA PTER II
11.1 (a) 8. 1 X I()3J (b) 1.62 X 104 J
11.3 (a)60 J (b)70 J ,liberaled (e) Q._50 J , Q.. _ IOJ

11.7 (a) Q - a(T2 - TI) + b(T~ - 71)+ C(:2 - :)

(b) C~ .... - a+ b(T2 + TI ) - (ITIT,
(e) JlS _ a In (T,ITI) +2b{T2 - T I ) - cITIT, Absolute temperature, 444, 482 Bahner, J. (1825-1898), 117
(d) 24.0 X 103 J K - I mole- I, 23.6 X 103 J oK-I moie- I
Absorption edgc, 178 Bahner formula, 115
11.15 Sim' - - kN [k~ tanh (tlkT) - In 2 oosh (t/kT) ]; Absorption spectrum, 22 Band, conduction, 246
Acceptor, 266 valcnce, 246
Cv In' _ kN In 2 C08h (f/kT) Acoustical bra nch, 241 Barn, 290
11.19 (b) 224.5 cal OK- I Act.inium ae ries, 329 Barrier pcnctration, 80
11.21 (!I.) T _ (iJlf/iJS)., V _ (iJlfliJp)s (b) P - -(df'l iJV)r, S - - (iJFlaT)v Ac t.ivity, 332 Baryon, 378
(c) V _ (iJGliJp)r, S - - (aG/iJT). Adiabatic compressibility, 516 Usryon quantum number, 399
11 .23 AlllI.re exwnsive except for p, T, and (iJllliJS)., wh ich are inwl1llive. Adiabatic demagnetizatio n, 486 Benzene (Cull G) mo\CCule, 211, 279
11.27 JlS _ LI T _ 5.28 cal K- l mo le- I; 1/ - L - 1440 cal mole- I ; Adiabatic tTlLnsformation, 474, 484 Bergmann aeriCll, 173
lJ.U _ lJ.H - plJ.V _ 1440.05 cal mole- I Alpha decay, 335 Ilerylli um, energy lcvels of, 175
AIIlha particle, 329 Beta particle, 329
11.33 3.49 X 1()3 J ; 3.49 X 1()3 J; 0; 0; 11.6 J oK- I
Ammonia (N H3) molecule, 202 lleta decay, 340
wave {unctiol1ll for inversion motion of, 85 Bethe cycle, 365
energy levels, table of, 87 Ilindiug energy, 76
C II APTER 1%

12. \ lV - NRT In (V,/ Y.) - N'(RTb - a)(~2 - ~J+

2
... ;
1427.3J
AndeT!tOn, C. (1905- ),380
Angular momentum, conservation of, 403
nuclear, 288
nuclear, 293
Ulackbody radiation, 8, 531
Bloch's theorem, 25 1, 259
12.5 (a) II:r _ l i p (b) 11:1' _ y2(V - NW/{NRTy3 - 2N a(Y - Nb)'} quantization of, 1t 8 Bohr, N. (1885-1962), 22, 117
12.7 (a) pIT-I)/T T _ C (b) Ty, - I - C spin, 135 Bohr formu la, 22
12.13 (b) T.V1 - 1 _ T2V; - I, T2 _ 212K, T3 - 88.5 OK (e) 3.Z5X 104J total, 135, \64 Bohr magneton, 133
Angular wave functions, 123 Bohr radiulI, 11 3
12. 15 (b) Wl2 _ 16.00 X lOs J ; lV23 _ 0; lV31 - - 13.02 X lOs J; lVr - 3.88 X 105 J ,
IlS12 _ 5.39 X 103 J oK- I,lJ.S23 _ - 5.39X I()3JoK - 1;lJ.S31 - O;IlST - 0 Annihilation, electron pair, 381 Boltzmann, I,. (1844- 1906), 11,436,
proton-anliproton,381 482
12.17 T _ 9,, 1 - 0 :36.9%,1- I: 43.2%; 'r - 29,,1 - 0:30.2%,1 - 1:55.3% Antiparticle, 379 Boltzmann constant, 444
12.19 1.2 X 10" molccules of II" 2.65 X 1021 moleculcs of Ch Antiproton, 385 Bond, covalcnt, 198
Antincutrino, 341 ionic, 198
Anti-8tokes line, 221 .,,- and "", 205
C II APTEU 13 Associated production, 402 Bom, M. (1882- ),239
Atmosphcre,465 BO$C, S. (1801- ),528
13. 11 2.20kT 13.27 2.09 X 10- 7
Atomic mass, 286 llo.sc-ginstcin dislribution law, 529
Atomic mass ullit, 286 Uoilon, 51!), 528
Atomic number, 109,283 masslCll8, 378
Auger effect, 178 Boyle'!! law, 465
589
I
f lldt:r; 591
5!10 1I!d~:t

Dalitz diagram, 560 Eleetron-p<.;;ilroll pair, 32

Boyle tcm])Crllture, 615 Conductivity, 269 Elcmentary IIRrtielc, 377
Davisson, C. ( 1881- 1956), 36
Ilrackcll seriC!l, 11 G intrinsic, 265 de Broglie, L. (1892- ),33 Emi!!tion, field, 84
Bragg condition, 36 Conductor, 261 I';I)()ntanCO\l.~, 95
de Broglie wa\'elcngth, 33
Bragg $Caltering, 253 Configuration, 158 stimulated, 95, 534
Debre, 199
Brenll!Strahlung, G Conjugated molecule, 208 thermionic, 526
Debye-Sehe rrer patterns, 35
Brillouin ron~, 253 Consen'ation, of angular momentum, <103 Emi!!lioll ~pe<: tru m , 22
Debye temlloerature, 53S
Bubble chamber, 572 of baryons, 399 Emittance, radiation, I I
Decay, !l1)()nl.llncous, 386
Hulk modulus, TIS, 516 of charge, 404 Deeay modes of unstable fUl"ticles, 380 Energy, binding, 76
isothermal, 488 of energy, 4().1 chemical, 466
Decay probabili ty, 332
of isotopic spin , 399 conlleT\'ation of, 401
Degel1erncy, 688
Calcium, energy levels of, 174 of leptons, 398 di!!tQCiation, 76
essen tial, 119
Calorie, 466 of momentum, 403 equipartition of, 5 13
eschange, 152
Carbon cycle, 365 of I13rity, 406 Degeneration , gas, 5-11 Fermi, 249, 521
Carbon, energy levels of, 168 of particles, 63 Degree Kelvin, 444, 496 internal,462
Carbon dioxide (CO,) molecule, 219 of strangeneS.'!, 402 ioni .alion,76
Degree of freedom, 512
Camot cycle, 485, 496 Contact potential difference, 527 mo~t probable, 455
Deuterium, 365
Carnot'~ t\u..'(Hcm, 486 Continuous energy spectrum, 24 qlllllltization of, 65
Deu teron, 293, 301
Cercnkov COUlltcr, 571 Coolant, 362 to tal internal, 463
Diamond, 232
C-frllillc of reference, 29, 555 Correspondencc principle, 121 zero-l)()int,6i
Die terici equation, 516
Chl"ldwick, J. (18IH- ), 3M Cosmic ray, 393 Diffusc series, 173 E nergy bnnd, 245, 262
Chamber, bubble, 572 Coulomb excitation, 28, 320 Energy co m:ctioll, relativistic, 131
Diffusion, 476
e\oud, 366, 571 Coulomb integral, 158 Energy density, monochromatic, 7
Dil)()le moment, electric, 6
ioni~ation, 366, 56!! Coulomb scattering, 308 Etlcrgy filter, 37
magnetic, 289
spark , 573 Counter, Ccrenkov, 57 1 Energy level, 23, 65
Disinteg ration eonst!!.nt, 330
Chain reaction, 362 Geiger-:\ Iiiller, 569 Ellerg)' w idth, 44
Dissociation, 30
Ch:mge of l)hase, 490 proportional, 569 Di$SOCiation energy, 76, 201, 216 Enthalpy, 474, S04
molar heaL of, 491 scintillation, 565 D is.tribution law, Bose-Einstein, 529 Entro\l)",475
Characteristic tCnll)C rature, for rotation, Covalent bond, 1!lS EtltrollY, ideal gu, 478
Fermi- Dirac, 521
506 Covalent solid, 231 :\laxwell-BoItZffiallll, 439, 445 F..tjuation of state, 469
for \'ibral;oll, 509 CI' operation, 410 Equation of sta te, Dieterici, 516
Donor, 266
Gh:ugc conjuga.tion, 409 CPT operation, 411 Doppler shift, electromagnetic, 45, 51 ideal gas, 495
Charge-e:u;h9.l'lge COlliSiOll, 184, 188 Critchfield cycle, 366 real gu, 497, 50 1
Doublet, 87, 139
Charge reflection, <1M CI"O$'! section, 350 Drude-Lorenu. theory , 270 sys tem, 49.5
C1R]>eyron's equation, 491 differential, 304 Dulong- Petit law, 539 van der Waals, 515
Cloud chamber, 366, 571 macroseol)ic, partial and lotal, 33, 351 Equilibrium, statistical, 435
Coefficient of cubicRI eXI13llsion, <188, sca ttering, coulomb, 30S thermal, 449
Edge dislocation, 238
515 macroscopic, 272 Equilibrium partition, 440
Effeeti\'e mllM, 257
Collcctive rotation, 319 total,306 Eflieiency of a thermal engine, 486 Equiparlition of energ)', 513
Collectivc vibr!!.tion, 319 CrystRI, ionic, 232
Effusion, 454 Equivalent electron term~, table of, 166
Colli.~ioll, inel{l...qtic, 27 Cryslallanice, 231 Eightfold way, 422 Erro r function, 458
Color ccntcr, 276 Curie, 332 Einstein, A. (l 879-i!:I55), 12,533 E!llSCntial degeneracy, 119
Commutator, 107 Cu rie, P. (1859-1006) and:\1. (1867-1934), Ethane (lh0-Clh) molecule, 205
Elastic scattering, 349
Compound llucleu$, 31!) 332 Electric dipole, 6 Ethylene ( l'I ~0-C Ii2) molecule, 205
Compre!l.;;ibility, adiabRtic, 510 Cycle, 468 Electrical permittivity, 280 Exchange degeneracy, 152
Compton, A. (1892- 1902), 15 Bethe or carbon, 365 l~sc hRnge integral, 158
Eleclroll , 377
Compton effect, 15 Carnot, 485, 496 Electron capture, 341 Excitation, coulomb, 28
Compton wavelength, J(l Critchfield or proton-proton, 365 Excitations, collective, 319
Electron gas, 522
Condon, E. (1002- ),221 nitrogen,3i 5 Electron Ilair production, 381 Exci tntion energy, 27
Conduction bRnd, 2U.i CyClical tran sformation, 468
 59'
Exeiusion priucipl(!, IS!)
EXlllillsion ratio, 465
":"pcct:&lioll \'1I.1uc, 100
External work, 467
F -centers, 276
Fermi, E. (1001- 1954), 343, 519
Fermi-Dirac distribution law, 521
Fermi energy, 241), 521
Fermi temp('rature, 522
Fermi velocity, 273
Fermion, 100,378,5 19
Field , electromagnetic, 4
malter, 33
Fie ld electron emiSSion, 84
F iue structure, 156
J<'inc structure eonst.an~, 132
Fi rst law of thermodynamictl, 467
Fi rslrgcnerQ.liOIi star, 310
Fi8Sioll, 296, 357
Spontaneous, 359
fourier analy~i~, 39
Frame of reference, CCIlU! r of
C-fnuIlC, 29, 555
labortl.lory o r I...-fmrnc, 28
Franck, J . (1882- ),:n , 224
Franck-Condon princi[lic, 224
.Free elec lron model, 246
Free energy, Gibb.!, 400
HclmholtJ, 489, 490
Free CXlliI lls ion, 478
Fundamental particle, 345, 377
Fusion, 363
Fusion, heat of, 490
Gamma ray , 320, 329
GILi, e lectron, 522
phonon, 537
l)hoton,531
GW! constan t, 452
Gas degeneration, 541
GII.'J thermometer, constant volume 496
Gauge transformation, 4<14 ' spectrum of, 115
Gciger-Muller eountcr, 569
Gelt-Mann, 1\1. (1929-- ),422
Gerade, 192
Germcr, L. (18%- ),36
Gibbs, J. (183!H903), 436
Gibbs free cncrgy, 490
Jmkz 593
Grand partitiou fUllctioll, 498 Ice, 235 j-j coupling, 158
Grand parti tion function, rea.1 gas, 498, Ideal gW!, energy distribution in, 453 J oule effect, 271
SOl Ideal gM entropy, 478 Junction , p-n, 266
Graphite, 236 Ideal monatomic gll.:'l, partition function, 451
GravilOn,377 I mpsc t parameter, 304 Kann, 389
GrouI) velocity, 254, 560 I mpoC.rfeclion~, 238, 272 Kernel,171
Gyromagnetic mlio, 135 Imlmrity,238 Kilocalorie per mole, 226
nuclear, 290 I ndependent-particle model, 15 1 Kinetic cncrgy, internal, 463
s pin, 289 I nellLitic !!Catteriug, 349 Klein-Go rdon equation, 148
Jnsulalor, 261
Hadron, '100 I.ntensity, wave motiou, 54 Laguerre polynomial, associated, 146
Halflife, 331 I ntensive variable, 400 Lamb shift, 142
Half-value thickness, 50 I nteraction, clectromagnetic, 4 Lnnd~ faclor, 143
Hall effect, 28 1 nuclear, 283, 298 Langevin's formula, 447
Ibmiltonian,97 residual,315 Laser, 534
sl)in-orbit, L39, 312
Harm oni c oscillator, quantum mechanical Lattice, 231
"
Heat, 464, 466
. strong, 283
\<ihrtltion-rolation, 219
Latlice momentum , 255
Lattice vibration, 240
Heat capacity of gases, con~tant pressure, weak,345 Laue SlJO t patlern, 35
474, 50~ I nternal energy, wtal, 463 LCAD (linear combination of alomic
I nterstitial atom , 238
oolU!tant volume, 473, 504 orbitals), 18 6
Heat capacity of so lids, 536 Intrinsic conductivity, 265 Lee, T. (192&- ), 406
lila&! or Heat capll.City mtio, 505 I ntrinsic probability, 438, 519 Legendre polynomial, 115
Heat of fusion, 490 Ion, 109 Lepwn , 378
Heat of vapo ri~ntion, 490 Ionic bond, 198 Lepton quantum number, 39i:I
Belicity ,380 Ionic crystal, 232 J.... rrame of reference, 29
Helium- II , 541 Ionization chamber, 569 Lifetime, 44
Helium, energy levels of, 156 IOlliJation energy, 76 a\<eragc, 95
Helium burning, 369 of the ele men ta, 159 Line spectrum, 115
Uelmholtz free cnergy, 489, 490 Ionization potenti:, I, 31 Linear absorption coeffieicnt, 33
Ionosphere, 31 Lorentz transformation, 553
HeiSO:llberg, W. ( 1901- ), 40
Heisellberg uncertainty I)rincipic, 40 IrrcveT!lible transformation, 470 1....8 coupling, 164
Isentropic tran~formation, 475 Luminescence, 276
Hermite polynomial, 103
Hermitian, 97 Isobar, 284 Lyman scriCll, 1J(I
He rtl, G. (1887- ), 'IT l.'\Obaric spin, 400
Hertz, II. ( 1857- 1894 ), II Isobaric transformation, 473 Macroscollic CI"088 sec lion, 33, 351
Hole, 258 Isobars, nucleon, 423 Macroscopic scattering CI"OSll .!!Cction, 272
Hund 's rule, 163, 167 l sochoric t ransfo rmation, 473 l\ladclung constant, 239
Isomer, 323 Magic number, 31 1
Hybridization of wave functions, 20.'
Hydrogen atom, 1()9 Isomeric transition, 323 Magnctie dil>ole moment, 289, 317
Hydrogen, cnergy levels of, III Isomerism, islallds of, 323 orbital, 132
radial wave fuuetiorul of, 125 1SOSllill, 400 s pin, 135
Isothermal bulk modulu.s, 488 Magnelon, Bohr, 133
Hydrogen-bond so lid ~, 235 Isothermal transformation, 474, 484 nuclear, 289
Isotone, 284 Main so:qucnce star, 370
Hydrogen chloride ( li CI) molecule, 2 15, 218
Isotope, 284
Hydrogeu ( R ~) molecule, 194 Maser, 534
Hydrogen molecule ion (II;), 183 Iso topic spin, conservatio n of, 300 MII.S!I, effective, 257
l lyperehnrgc, 402 Isotopic s pin rotation, 104 MB3S defect, 373
Hyperfine splitting, 325 Iso topic IIpin space, 400 Mas!Il\umhe r, 109, 283
59!' I ndu 595

Mathiesscn's rule, 273 Neutrino detection experiment, Cowan- Parahydrogen, 225 PreMure, 464
Matrix elements, 101 ReinCll, 345 Paramagnetism, Pauli spin, 250 aero-point, 541
MaHer field amplitude, 54 Neutron, 37i Parity, 88, 293, 314, 405 Principal series, 173
l\laximum overlap, principle of, 202 discovery of, 354 nonconservation of, 'lOS Principle of cquiparlition of energy,
:\laxlO'ell, J, (1831 - 1879), 436 Neutron eapture, 351 Parity oper&tion, 410 '13
Principle of maximum overlap, 202
Maxwell-Boltsmann distribution law, 439, Neutron detector, 570 Partial ""a,'e, 304
4<, Neutron diflrtl.ction, 36 Particle, fundamental or elementary, Principles of quantum mechanie;<, 98
l\laxwell relations, 400 Nitrogen cycle, 375 Probability, 55
i\ laxlO'ell's formula for an ideal glU, 452
l\1 ~ic alOm, 411, 427
Noise, 536
Nonconservation of parily, ~OS
'"
identical, 436, 519
\'irtual,421
intrinsic, 438, 519
state, 519
Meson, 378 Normal modes of vibration, 219 Partition, equilibrium, 440 transitioll, 44 , 94
Metal, 236, 262 Normalization, 56, 67 most probable, 435 Probability deneily, 55
Metastable state, 121 n-type semiconductor, 266 Partition function, 439 J'robability of distribution, 434
l\lethanfl (CH 4 ) molecule, 20~ Nuclear angular momentum, 288 grand,498 Production, a.sso<:iated, 402
l\l irror Iluelei, 297 Nuclear binding energy, 293 ideal monalOmic gas, 45 1 pair, 383
1\10 (molecular orbital), 186 Nuclear gyromaglletic ratio, 200 Paschen series, 116 Proper fun ction , 96
l\ loderator, 362 Nuclear interaction, 283 Pauli, W. (WOO-19SS), 159 Proper value, 96
Mola r heat of change of phase, 491 Nuclear magnetic dipole moment, 317 Penetrating orbits, 127 Proton, 377
Mole, 452 Nuclear magncton, 289 Pfund series, 116 Proton-proton cycle, 366
Molecule, 183 Nuclear riLuiWl, 287 Phase, changc of, 490 p-type semiconductor, 266
acetylene, 207 Nuclcar reaction, 348 Phase shift, 79, 306 p-V diagram, 471
ammonia, 202 Q of a, 350, 374 Phase space, 42
benzene, 211 Nuclear react(lr, 362 Phonon, 243 Q of a nuclear reaction, 350, 374
beta-earotene, 228 Nuclear spin, 288 Phonon gas, 537 Q-equation,558
butadiene, 208 Nucleon, 283 Phosphorescence, 277 Quadrupole moment, electric, 290, 325
conjugated,208 Nucleon isobars, 423 Photoelectric effect, 12, 526 Quantization, energy, 65
ethane, 205 Nuclcus, compound, 340 atomic, 31 Quantum number, baryon, 399
ethylene, 205 daughter, 329 Photofission,358 lepton, 398
heteronuclear, 107 Nuclide, 283 Phowgraphic emulsion, 573 Quark,420
homonudear, 102 Photoionilation,31
hydrogen, 104 Ohm's law, 269 PhOlOn, 18, 377 Radial SchrOdinger equation, 130
methane, 2O~ Omega-minWl experiment, 423 spin of the, 379 Radial wave function, 125
oxygen, 197 OperalOr,96 virtual, 421 Radiation, blackbody, 8, 531
!!Odium chloride, HI7 quantum, table, 99 PholOn glU, 531 e!e<:tromagnetic, 5
water, 202 Optical pumping, 535 I'hotonuclear reaction, 32, 350 synchrotron, 5
Molecular rotation, 212 Orbital, atomie, 153 Pion, 377, 388 Radiation emittance, 11
Molecular solid, 235 molecular, 186, 192 Planck, i\1. (1858-1947),8 Radiation law, Planck, 9, 532
Molecular vibration, 215 Orbita! wave fun elions, !53 Planck radiation law, 9, 532 Radiath'e capture, 31
Morse potcntial, 199 Orthogonal, 97 Plasma, 364 Radiative transition, induced and
Moseley, H , (1887- HI15), 181 Orthohelium, 155 p-n junction, 266 spontaneous, 532
l\Hissbauer, n. (1929- ),46 Orthohydrogen, 225 Positron, 32, 340, 377 Radiative transitions in solids, 274
Mossbauer effect, 45 Overlap integral, 191 I'ositronium, 384 Raman, C, {188B- ),220
Multiplet, 166, 399 Oxygen energy levels, 169 Potential barrier, 80 Raman effect, 220
Multiplicity, 156, 166 Oxygen (02) molecule, 197 Potential box, 64 Hange, 73, 372
Multipole transition, 321 two-dimensional, \03 Ratio of heRt capacities, 505
Muonium,427 Pairing effect, 288 Potentia! energy, internal, 462 Rayleigh-Jean~ law, 48, 545
Pairing energy, 297, 315 l'otentin.1 step, 59 iteaction, chaill , 362
Ne'eman, Y. (1925- ),422 Pair production, 32, 383 Potential wall, 62 nuclear, 3018
Neutrillo, 343, 377 Parahelium, 155 Potential well, 73 photonuclcar,350
 IllIkz 597
596 Inda
Statistical e1luilibrium, 435 radinl wave functions, 125
Q of a, 350, 374 Semimctal,263 Statistics, Hose-Einstein, 519 ratio of heat capacities, 514
stripping, 349 Series, hydrogen, 116 Io'ermi-Dirac, 519, 522 rotational and vibrational constants in
Reactor, fusion, 364 radioactive, 329 Maxwell~l3oltzmann, 436 diatomic molecules, 2 13
nuclear, 362 Sharp scries, 173 Stefan, J. (1835- 1893), II Hydberg constant, 112
Heal gas, equSlion of ~tate for a, 497, 501 Shell model, 310 Stefan~B()ltlmann law, II stable and 10ng~livcd nuclides, 315
grand I)lHtilion function of a, 498, 501 independent--particle, 315 Stern-Gerlach experiment, IJ5 strangcness of mC!!OIlS and baryOllll, 400
Red giant, 3iO Singlet, 154 Stimulated emission, 95, 534 terms for equivalent electrollll, 166
Reduced mllll8, 112 Slater, J. (1(100-- ),170 Stirling's formula, 440, 563 thermionic constant, 527
ReRection coeffieieut at a ]lOtenlial stel), 63 Sodium, fine struelure of, 174 SLOke!lline, 221 threshold energies for photofission, 358
Relative abundance, 367 Sodium chloride (NaCI) molecule, 107 StrangenC!l8, 402 uranium serie!l, 331
Relaxation time, 270 Solid, covalent, 231 Stripping reaction, 34.9 van der Waal;s cons tants, 503
Residual resistivity, 273 ionic, 232 Strong intersction, 28J vibraliollnl energy levels of Nih
Resistivity, 269 hydrogen~bond, 235 molecule, 87
Resonance, 22, 35 1, 377, 414 molecular, 235 Table, angular momentum stale wave func lion ~ of a harmollic oscillator,
RC&Jnsnce absorption, 45 Sound velocity, 536 designations, 118 72
Rest energy, 554 Space quantization, 118 angular wave functions, 123 work function, 527
Richa rd&Jn-Duslull(1n equation, 527, 544 Spark chamber, 573 bond lengths in diat.omic molecules, 199 Temperu.ture, 405
Rotation, characteristic temperature of, 506 Spectrum, absorption, 22 characteristic temperature for nbsolute, 444, 482
kinetic energy of, 213 band ,218 rotation, 508 Boyle, 515
molecular, 212 continuous and discrete, 24, 76 characteristic temperature for vibration, characteristic, for rotation, 506
Russcll-Saundel'll eouliling, 165 emission, 22 508 for vibration, 509
Rutherford, E. ( 187 1- 1937), 3 10 line, 122 Dcbye temperatures, 538 Dcbye, 538
Rydberg constant, 110 x~ray, 21 dissociation ene rgies in diatomic Fermi, 522
Spherical harmoniCII, 122 molecules, 199 mcasurement of, 4!15
Sackur--Tetrode equation, 478 Spin, electron, 135 effective m'-Sll, 257 n<'gative absolute, 483
Saturation, 296 i&Jbaric or isotopic, 400 electric dillOle moments in diaLOmic thermodynamic, .j!l7
Scattering, 349 nuclear, 288 molecules, 199 Term,IGS
Bragg, 253 Spin gy romagnetic ratio, 289 clcctrollic configurations of al.Oms, 162 molecular ground ~ tate, 200
coherent. or Rayleigh, 221 Spin-orbit interaction, 139,312 electronic configursliolls of homonuclear Thermal engine efficiency, 486
elastic and inelaSlic, 349 Spin space, isotopic, 400 diatomic molecules, 196 Thermal equilibrium, 449
neutron-proton, 303 Spin wave functiollll, 154 electronic state designations, 130 ThcrmAI neutrons, 37
Raman, 221 Splitting, hyperfine, 325 energy correction for nuclear motion, 115 Thermal oscillatory motion, 372
Scatlering aml)litude, 304, 326 SpontancoWl decay, 386 energy levels and degeneracies in a Thermionic emission, 526
Scattering CJ'Ol!S seelion per cente r, 273 SponuUlcoWl emission, 95 cubical box, 69 Thermod ynamiC lIurface, 469
Schmidt lines, 318 Spontancous fission, 359 energy galJ1!, 265 Thermodynamic temperature, 497
SchrMinger, E. ( 1887-1961), 66 Spontaneous radiati,'e tranSition, 532 error function, 459 ThermodYllamics, 462
Schrodinger equation, 56 s-scattering, 307 essential degeneracy, 118 first law of, 467
radial, 130 Star, first--generation, 370 Fermi ellergy, 2-t!I, 524 !'CCond law of, 476
relativistic, 148 main sequence, 370 Fcrmi temperature, 524 lerolh la .... of, 449
time-<lcpendent, 00 red giant, 370 fissionability of heavy nuclei, 358 Thermometer, 495
Scintillation counter, 565 second-gene ration, 370 fUlldamental pllTticies, 378 g&.~, 4!16
Scinti1!aLion spectrometer, 567 State, bound and unbound, 112 hypercharge and i&Jl.Opic 81)ill of mesons Thomson, G. (1802-- ), 35
Second-generation star, 370 equation of, 469 all d baryons, 400 Thorium serie~, 329
Second law of thermodynamics, 476 excited and ground, 22 pnrtic!e decay mooes, 387 T hreshold energy, 393
Selection rule, 04, 120 metastable, 121 prolJCrties of fi>!Sionnble materials, 360 Th reshold kineUc energy, 28
electric..dipole transition, 168 molecular, 192 prOIJCrties of nuclides, 291 Tight--bindillg allproximatioll, 259
Self-consistent field, 435 stationary, 23, 92 qunntum o)JCrnlOnl, 99 Time, relaxatioll, 270
Semiconductor, 261 State probability, 519 Q~value for different 232U decays, 340 T ime rever.<al, 410
n-t.ype and J}-t.ype, 266 Stationary state, 23, 92