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1 Chapter

The basicsof quantum mechanics

1.1 Why quantum mechanics is necessary for describing molecularproperties

we krow that all molcculesare made of atoms which. in turn. containnuclei and electrons. As I discuss in this introcjuctory section, the equations that govern the motions of electrons and of nuclei are not the familiar Newton equatrons.

but a nervset of equations calledSchrodinger equations. when scientists first studiedthe behaviorof electrons and nuclei.thev tried to interprettherr experimental findin-ss in termsof classical Newtonian motions. but suchatrempts eventually failed.Theyfoundthatsuchsrnalllightparticles behaved in a waythat simply is not consistent rvith the Neu'tonequations. Let me norvillustrate sorne ofthe experimental datathat gaverise to theseparadoxes and shorvyou how the scientists ofthoseearlytimesthenusedthese dataro suggest new equatrons that theseparticlesrnight obcy.I want to stress that the Schrcidinger equationwas not derivedbut postulated by thesescientists. In fact,to date,rlo one hasbeenable t o d e r i r et h e S c h r c i d i n ge eq r uation. Fron.r the pioneering work of Braggon ditrraction of x-raysfiom planesof atomsor ions in crvstals, it was knownthat peaksin the intensity of ditliacted x-rays havin,u wavelength g determined i rvouldoccurat scattering angles by the larnousBragg equation:
nt : 24 tinp


where d is the spacingbetweenneighborin,u planesof atomsor ions. These quantities are illustratedin Fig. I . I . Therearemany suchdiffractionpeaks,each l a b e l e d b y a d i f f e r e n t v a l ute ho efi n r e g e nr (n - 1,2.3,...).TheBra-s-qformula can be derivedby considering when two photons, one scattering from the second plane in the figure and the secondscattering from the third plane,will undergo constructiveinterference. This condition is met when the ,.extrapath leneth,'

The basics o f o u a n t u mm e c h a n i c s

Scattering of t w o b e a m sa t a n g l e6 f r o m t w o p l a n e si n a crystalspacedby d.

photon (i.e.,the lengthfront pointsA to B to C; is an covered by the second integer multipleof the wavelength of the photons. The importance of these x-rayscatterin_e experiments to the studyof electrons and nuclei appearsin tl.reexperirnents of Davissonand 1927, u'ho scattered electrons of(reasonably) fixedkineticenerg)' E from metalliccrvstals. These workers foundthatplotsofthenumber ofscattered electrons asa function of "peaks" scattering angle d displayed 6 thatobeyed atangles a Bragg-l ikeequation. The startling thing aboutthis observation is that electrons are particles. vet the Bragg equationis basedon the propertiesof waves.An important observation derivedfron.r the Davisson-Germer experiments was that the scattering angles6 observed for electrons of kinetic energ.v E couldbe fit to the Braggni, : 2d sin0 equationif a wavelength were ascribed to theseelectrons that u'asdefinedby )":hl(2m"E)t'2. (1.3)

where rl. is the massof the eiectronand i is the constantintroducedby Max Planckand Albert Einsteinin the eariy 1900s to relatea photon's energv,Eto y its frequency I'ia .E : /rt,. Theseamazing findingswere amongthe earliestto suggest that electrons, u,hich had alwaysbeen viewed as particles,might have somepropertiesusually ascribedto waves.That is. as de Broglie suggested in 1925,an electronseems to havea wavelength inversely related to its momenfum, andto displaywave-type diffraction.I shouldmentionthat analogous diffraction u'asalsoobserved whenothersmalllight particles(e.g.,protons. neutrons, nuclei, and small atomic ions) were scattered from crystal planes.In all such cases, Bragg-likediffractionis observed and the Bragg equationis found to governthe scattering angles ifone assigns particleaccording a wavelength to the scattering to ),:hlQmE)1t2, (1.4)

where rl is the mass of the scatteredparticle and /r is Planck's consranr ( 6 . 6 2x l 0 - 2 7e r gs ) .

i s n e c e s s a rfyo r d e s c r i b i n g properties molecular W h y q u a n t u mm e c h a n i c s



Anarvsis lrrn Llf

I VisibleI




Emission spectrumof atomic hydrogen with some lines repeatedbelow to illustrate the series to w h i c ht h e y b e l o n g .

Theobservation thatelectrons andothersmalllight particles display ivave-like r.vas important behavior particles because these arewhatall atomsandmolecules are made of. So, if we want to fully understand the motions and behaviorof rvemustbe surethat*e can adequately molecules. describe suchproperties for theirconstitr"rents. Because the classical Newtonecluations do not contain tactors that sr-rggcst wave propertiesfor electrons or nuclei mo'",ing freely in space.the abovebehaviors presented significant challenges. Anotherproblemthat arosein earlystudies of atomsand molecules resulted fiom the stLrdy of the photonsemittedfrom atomsand ions that had beenheated or otherr.ise excited(e.g.,by electricdischarge). It was found that eachkind of atom (i.e.,H or C or O) ernitted photons rvhose frequencies u wereof very characteristic values. An example of suchemission spectra is shownin Fig. I .2 fbr hydrogen atoms.In the top panel,we seeall of the linesemittedwith thcir wavelengths indicatedin nanometers. The other panelsshow horvtheselines (by scientists havebeenanalyzed rvhose narnes areassociated) into patterns that relateto the specilicenergylevelsbetween which transitions occurto emit the corresponding photons. In theearlyattempts to rationalize suchspectra in termsof electronic motlous. one described an electron as rnovinsaboutthe atomicnuclei in circularorbits such as in Fig. 1.3.A circularorbit was thoughtto be stablewhen the outwardcentrifugal fbrcecharacterized by radius r. and speed u (rr.u2/r) on the perf-ectlir electron counterbalanced theinwardattractit,e Coulombforce(Ze2 l121 exerted by the nucleus of charge Z:
n.r- ,'t' = Ze-lt .

(1 . 5 )

This equation,in turn, allows one to relatethe kinetic energy lrr.ul to the Coulornbic energyZe2 the t o t a le n e r g y E o f a n o r b i ti n lr, and thusto express

T h e b a s i c so f q u a n t u mm e c h a n i c s

terrnsof the radiusof the orbit:

E : I - rtt..r- Zt'-,r' :
f ' '

-l Z L ' -/ t ' .


Characterization of small and large stable orbits of radii 11 and 12 for an electron moving arouno a nucleus.

The energycharacterizing an orbit ofradius r. relatil'eto the 6 : 0 reference --+ (i.e.,lorverandlou,er)asr of energyat r 3p. becomes more andmore negative becomes smaller. This relationship between outu'ardand inu,ardforcesallou's that the electronshouldrnovefasteras it movescloserto the one to conclude : r'2 nucleus since Ze7l(rntr). Howeter.noq'here in this mclclel is a concept that relates to the experimental fact that eachatoll erltitsonll'certainkindsof u'asbelieved thatphotoner.nission uficn an electron r.rrovirrr occurred irr a largercircular orbit lostenergy to a sn.raller andnroved circularorbit.Hor.r'ever. the Newtonian dynamics thatproduced r.vould the above equation allou'orbrts of any radius. and hence any energy. to be follorved. Thus"it wouldappcar tlratthe electron shouldbe ableto emit photonsof any encrgyas it movedfi'omorbit to orbit. The breakthrough that allowed scientists such as Niels Bohr to apply the circular-orbitmodel to the observedspectraldata invol','ed first introducinsthe ideathat the electron has a wavelength i is related and that this u'avelensth to its nromentum by the de Broglie equation L- hlp. The key stepin the Bohr model u'asto also specifythat the radiusof the circularorbit be suchthat the (n) multipleof theu'avelen-gth cilcurnference of the ctrcle2nr equalan integer i. vu'ave Only in this way will the electron's experience constructive interference as the electronorbits the nucleus.Thus, the Bohr relationship that is analogous to the Bragg equationthat determines interference at what anglesconstructive can occuris 2 t r r: n ) . . (1.7)

Both this equationandthe analogous Braggequation are illustrations of what we call boundaryconditions;they are extra conditionsplacedon the wavelength to producesomedesired ( character in the resultant wave in thesecases, constructile interference). Of course,there remains the questionof why one must impose theseextra conditionswhen the Neu,toniandynamicsdo not requirethem. The resolutionof this paradoxis one of the thingsthat quantummechanics does. Returningto t h ea b o v e a n a l y s ia s n du s i n g l,: hlp: hl(mv).2rr :4)',sg weli as the force-balance equationm"r2 1, : Z e2 I 12, one can then solvefor the radii that stableBohr orbits obey:
y :1nhl2n)2 /(m"Ze2) and, in turn. for the velocities ofelectrons in these orbits,

(l 8)

v : ze2 lfuhl2tr).

(l . e )

i s n e c e s s a rf yo r d e s c r i b i n g properties molecular W h y q u a n t u mm e c h a n i c s

the sum ofthe k i n e t i c( l r r . r ' : ) a n c l Thesetrvo resultsthen allorv one to express (-Ze2 lrl energies as Coulombpotential g : - ! r , , z t r ' 1 t n l1 t 2 t1 ' . ) '


Just as in the Bragg diflraction result,rvhich specifiedat what anglesspecial occurredin the scattering, there are many stableBohr orbits. high intensities value the integer of ir. Those with small n have small each labeledby a radii. high velocitiesand more negativetotal energies(n.b., the reference to the electronat r : oc, and with v :0). So. zero of energycorresponds that result only certain orbits are "allowed" that causes the only certain is it to occur and thus only certain energiesto be observedin the emitted energies photolls. It turnedout that the Bohr formula for the energylevels(labeledby r) of could be usedto explainthe discrete line an electronmoving abouta nucleus s p e c t r o a f r l l one-electro an toms a n d i o n s{ i . e . . H. He . Li-:. etc.)to emission in suchan interpretation veryhighprecision. of theexperimental data. oneclaims that a photonof energy



is emittedrvhenthe atom or ion undergoes a transitionfiom an orbit having quantum number ni to a lower-energy orbit havingnf. Herethe symbolR is used to denote the fbllo*ing collection of factors:
R I -nt,Z-e*llltr)tl'


The Bohr formulafbr energylevelsdid not agreeaswell w ith the observed pattern of emission for species spectra containing morethana singleelectron. However, it doesgive a reasonable fit, for example. to the Na atomspectra if oneexamrnes only transitions involvingthe singlevalenceelectron. The primary reason for the breakdorvn of the Bohr formulais the neglect of electron-electron Coulomb repulsions in its derivation. Nevertheless. the success of this modelmadeit clear thatdiscrete emission spectra couldonly be explained theconcept by introducing thatnot all orbitswere"allowed". Only special orbitsthatobeyed a constructiveintert-erence condition werereallyaccessible to the electron's motions. This idea that not all energies rverealloweclbut only certain "quantized" energies could occur was essential to achievingevena qualitativesenseof agreement r.vith the experimental fact that emissionspectra werediscrete. In summary, two experimental that observations on the behaviorof electrons were crucial to the abandonment of Newtoniandynamicswere the observations of electron diffractionand of discrete emission spectra. Both of thesefindings seem to suggestthat electronshave some wave characteristics and that these waveshaveonly certainallowed(i.e.,quantized) wavelengths.

T h eb a s i c s o f q u a n t u mm e c h a n i c s

fail to accountfor So. nou, rve havesome idea why the Newton equations and nuclei. nrotions of light and small;lartrcles suchas electrons the dynan.rical (e.g..the Braggconditionor constraints on the de We seethat extraconditions u'ith degree of agreenrenl couldbe imposed to achievc some Brogiieu'avelength) r.i Hou'e'u'er, u'estill arelcft wondering hattheequations observation. experimental and why the extra such are that can be appliedto properlydescribe areneeded. It turnsoutthata ner.r'kind of equation based on cornbining conditions properties to address suchissues. These u'ave andparticle needed to be developed to ri'hichwe no\\'tunr our attention. arethe so-called Schrddinger equations no one hasvet shownthat the Schrodi-qer equation follou,s As I saidearlier. from somen.rore That is. scientists did not dedeductivelir fundamental theory. rive this equatiotr; theypostulated it. Sorre ideaof hou'the scientists o1'that era "dreamed the had thc tirre and up" Schriidinger equation can be by exan-rir.ring thatcharacterizes traveling u,aves. lt should be noted spatial depcndence so-called that the peoplervhoworkedon theseproblcmskneu'a greatdcal aboutu'aves (e.g.,soundw'aves and \\.ater \\'aves) they obeyed. Moreover. and thc equations of quantized they kneu' that u,aves could sometimes displaythe characteristic (e.9..fundamentals u'avelenqths and overtones in soundu'a'"'es). or fi'equencies for example. that r.r,a'u'es that are constrained at trvo They'kneu', in one dinrension points(e.g..a violin stringheld fixed at tu'o ends)undergo oscillatory motjon fi'equencies andu'avelengths. For exan.rple. in space andtime with characteristic just violin the motion of the string nrentioned as havingan can be described arnplitude A(r. t ) at a position-r alon-q its len-sth at tinle I gircn by l ( , 1 -/ .) : , 4 ( . r - . 0 ) c o s ( 2 . ' r y r ) . (1.13)

where r, is its oscillationfrequency. alsohas The arnplitude's spatialdependence givenby a sinusoidal dependence I (,r.0) : A sin(2r:;l).1. (1.1.1)

where.),is the crest-to-crest lengthof the rvave.Two examples of suchwaves1n onedimension in Fig. 1 these the is fixed areshown .4. In cases, string at x : 0 and : at x l, so the $,avelengths belongingto the two wavesshownare ), : 2L and ),= L.lf the violin string were not clarnped at ir: I, the wavescouid have any value of ),. Horvever. because the string is attachedat ir : l. the allowed u'avelengths are quantized to obey

)"= Lln. w h e r en : 1 . 2 , 3 . 4 , . . . T h e equation.reads


equation t h a t s u c hw a v e s thewave obey, called

Fundamenta aln d f i r s t overtone notes of a v i o l i ns t r i n g .


. d2A

(r . l 6 )

i s n e c e s s a rf yo r d e s c r i b i n g molecular properties W h y q u a n t u mm e c h a n i c s

wherec is the speedat which the wavetravels.This speeddepends on the comthe material from of which the violin position string is made.Using the earlier for the -r- and t-dependences of the wave,A(x,t). we find that the expressions andwavelength s frequency arerelated rvave by the so-called dispersion equation:
v : : ( c l n ) :.

(r . r7)

c: tv. (1.18)

implies,for example. This relationship that an instrumentstring made of a very (large material produce c) will stiff a higherfrequency tonefor a givenwavelength (i.e.,a givenvalueof n) thanwill a stringmadeof a softermaterial (smaller c). For waves moving on the surface of, for example. a rectaneulartwosurfaceof lengthsI,, and 1,,, one finds dimensional l(.r. r. /) = sinln,:r r I L.,)sin(n,:ry I L, )cos(2zur) (1.19)

Hence.the wavesare quantizedin two dimensionsbecause their wavelengths mustbe constrained to cause ,4(x.y. r) to vanishat_r : 0 and-r : Z. aswell as at -r,- 0 and,y : I,, for all times t. Let us now return to the issueof wavesthat describe electrons moving. The pioneers of quantummechanics examinedfunctionalforms similar to those shownabove. Forexample, fbrmssuchas I : exp[*22 i( ur - .y/i)] were considered because theycorrespond to periodicwavesthat evolvein -vancl t under no external,t'-or l-dependent forces.Noticing that
Jt.J ;(/.\- : - l /22 \r . l l

\ ,\ ,/


andusingthe de Brogliehypothesis X:

hlp in the aboveequation. one finds

.71.2 \l
\ tt /


, | ,a


If I is supposed to relateto the motionof a particleof momentum p underno externaltbrces(sincethe waveformcorresponds to this case),p2 canbe related to the energy E of the particle by E : p212m. So, the equationfor I can be rewrlttenas


'ti1 = -2,,r ('* )' ,,. n

\ /


or, aiternatively.

-(*)'#: uo

r t 1l\


T h e b a s i c so f q u a n t u mm e c h a n i c s

Returning to the time-dependence of l(.r'. /) and using v : Elh. one can also show that
/ h \ dA i ( ^ I ' : E i t '
\tlr / dl


which, using the first result.suggests that

th '\=/ 1d.4 :,t, r lt \:J:A ,.. \;/


This is a primitiveform of the Schrcidinger equation thatwe rvill address in much more detail below.Briefly, what is importantto keep in mind is that the use of the de BroglieandPlanclCEinstein connections E : lr,), bothof e,: h/p an<i which involvethe constant i. produces suggestive connections betrveen

,(+)# and E
and bet."veen
r D, anc 1/t1:d: \ 2:r) dt:

(r . 2 6 )

( 1 . 2| 7

or, alternatively. between

7.' and - , (:-'\ + \ :1T / .1.\


Theseconnections between phl,sical properties (energyf and mornentump)and differentialoperators are someofthe unusualfeatures ofquantum mechanics. The abovediscussion about wavesand quantized u,avelengths as rvell as the obser"'ations about the wave equationand differentialoperatorsare not meant to provide or even suggesr a derivationof the Schrodin_eer equation.Again the scientists who invented quantummechanics did not deriveits rvorkingequations. Insteadthe equations and rules ofquantum mechanics havebeenpostulated and designedto be consistent u'ith laboratoryobservations. My students often find this to be disconcerting because they arehopingand searching for an underlying fundamental basisfrom vvhichthe basiclarvsof quantummechanics follou, logicall1,. I try to remind them that this is not hou' theory u, uses experimental observation to postulatea rule or equationor theory,. and one then teststhe theory by making predictionsthat can be testedby further experiments. Ifthe theory fails, it must be "refined", and this processcontinues until one has a betterand bettertheory.In this sense. quantummechanics, with all of its unusual mathematical constructs and rules. shouldbe viewed as arising from the imaginationsof scientists who tried to invent a theory that was consistent with experimental dataand which could be usedto predict thingsthat could then be testedin the laboratory. Thus far, this theory hasprovenreliable,but, of course,

T h e S c h r o d i n g ee r q u a t i o na n d i t s c o m p o n e n t s

t l

"new and improved" theory that describes how we are ahvayssearchingfor a move. smalllightparticles of quantumtheory,I shouldpoint out If it helpsyou to be more accepting particles quantLrm description of will reduceto the classical Newton that the undercertaincircumstances. In particular, when treating heavypardescription masses and evenheavier atoms), it is oftenpossible to ticles(e.g.,macroscopic dynamics.Briefly. rve will discussin more detail how the quantum useNer,vton dynamicssometimes coincide(in which caseone is free to use and classical the simpler Neu,tondvnamics).So. let us now move on to look at this strar.rge that lve havebeendi-eressing equation aboutfor so long. Schrodinger

equationand its components 1.2 The Schrodinger

that electrons moving in atomsand molecules It hasbeenwell established do Newtonequations not obeytheclassical of motion.People long agotriedto treat nlotionclassicallv. electronic and tbundthat features observed clearlyin erperimcasurements mental simplywerenotconsistent with sucha treatment. Attentpts r,vere madeto supplcrnent the classical rvith conditions eqr-rartions that could be usedto rationalize suchobservations. For eraniple.earlvrvorkers required that theangular momentllm L : r x p be allowed to assume clnl,v integer multiples of l/22 (lvhichis ofien abbrcviated as fi), which can be shorvn to be cquivalenr to the Bohrpostulate tti : 2:rr. Hor,vever. until scientists realizecl thata ner',, setof those of cluantum rlechanics. appliedto light rnicroscopic particles. a rvide gullexistedbetr.leen laboratory phenomena obserlations of molecule-lcvel and thc equations uscdto describe suchbehavior. rnechanics is castin a languase that is not farniliar to moststudents Quanturn of chemistry rvhoare exarrininsthe subjectfbr the first timc-. Its nrathernatical content andhorvit relatcs to experimental measurements bothrecluire a -grc-at deal of eftortto mastcr. With these thoughts in mind.I haveorganized this ntaterial in a manner thatfirst provides a brief introduction to the two prirnary constructs of qLlantum mechanics operators andwavefunctions thatobeya Schrodinger equation.Next.I dcmonstratc theapplication of these constructs to several chemically relevant modelproblents. By learning the solutions of the Schrodinger eqLlatlon fbr a f'ewmodel systems, the str"rdent can betterappreciate the treatment of the fundamental postulates of quantum mechanics as well astheirrelation to experimentalrreasurement for whichthewavefunctions of theknolvnmodeloroblems off!r inrportunt inrerpr,.'rations.

1. 2 . 1 O o e r a t o r s
q u a n t i t yh a s a c o r r e s p o n d i n g E a c hp h y s i c a l l y measurable o p e r a t o rT , he e i g e n v a l u eo sf t h e o p e r a t o t re l lt h e o n l y v a l u e so f t h e c o r r e s p o n d i n p gh y s ical propertythat can be observed.


Thebasics o f q u a n t u mm e c h a n i c s

Any experimentally measurable physicalquantityF (e.g.,energy. dipole mo_ ment.orbitalangularmomentum. spin angularmomentum, linearmomentum, kineticenergy) hasa classical mechanicar expression in terms of thecartesian po_ sitions and momenta {q;} {p; } of theparticles thatcomprise thesystem of interest. Eachsuchclassical expression is assigned a correspondins quantum mechanical operator F formed by replacingthe lp1) in the classical form by the differentiar -i/1 0/0q operaror reaving the coordinates 1ar.rd in F untouched. 97 that appear Forexample. the classicar kineticenergy particles of y'y' (u,ithmasses r?1) movlnir in a potentialfield containingboth quadraticand rinear coordinate-def"nd.n.e can be written as


- q) ,) l t/2k( q1- ,tl) + t, ( q, l t'i /2 u ,,+

.F is


The quanturn mechanical operatorassociated with this

t :,I,

- +t'(q, -'ti')] L*,# * )r (,' q;')'

(I . 3 0 )

Suchan operator would occurwhen,for example, one describes the sum of'the kineticenergies of a collection of particles (the f,:, ,,(7ti plus rhe /2,,11rerm). sum of "Hooke'sLavu'''parabolic potentialstthe lfZy,,=t.t k(qr _ q!t'721, ana (the last term in F) the interactionsof the particles *itn ln .*r.rnaily appried field whosepotentiar energyvarieslinearryasthe particlesmoveaivayfrom their equilibrium positions {4,0}. Let us try more exampres. The sum of the:-components of angular momenta (recallthat vectorangurarmomenfurnL is defined as L : r x p; ota collection of ly' particleshas the following classical expression: t: f GiPvt-)'tP,i),


-/= I ..'\'

and the corresponding operatoris

t : -t,.,:.Iu (',* - r', +)

a 3Qi

( r. 3 2 )

If one transformsthesecartesiancoordinates and deri'ativesinto polar coordi_ nates, the aboveexpression reduces to F--iltf i?' ( 1. 3 3 )

The r--component of the dipole moment for a coilection of 1y'particles has a classical form of
\'p -- ./--


( r.34)

T h e S c h r o d i n g ee r quation and its components


for which the quantttmoperatoris F: I Z,exi,

(r .3s)

and *'here Z 1e is the chargeon theTthparticle.Notice that in this case,classical -F containsno momentumoperators. quantumforms are identicalbecause The mappingfrom F to F is straightforward only in termsof Cartesian coorTo map a classicalfunction .E,given in termsof curvilinearcoordinates dinates. (evenifthev are orthogonal),into its quantumoperatoris not at all straightforward. The mappingcan alwaysbe done in terrnsof Cartesiancoordinates after transtbrmation of the resultingcoordinates which a and differentialoperators to a curvilinearsystemcan be performed. quantum The relationship of these mechanical operators to experimental meaof the quantumoperators. surementlies in the eigenvalues Each such operator eg i g e n v a l ue eq u a t i o n h a sa c o r r e s p o n d i n

F x ,: u , x ,

(r . 3 6 )

in which the X7 arecalledeigenfunctions andthe (scalar numbers) cv;arecalled eigenvalues. All sucheigenvalue equations areposed in termsof a givenoperator (F in this case) and thosefunctions the function {X/} that F actson to produce (the eigenvalue). back againbLrt multipliedbv a constant Because the operator (coming from the momentum). F usuallir contains differential operators these equations aredifferential equations. Theirsolutions on thecoordinates X, depend thatF contains points. asdiflerential operators. An example will helpclarif,v these The differcntialoperator d f d.r' actson rvhatfunctions(of_r,) to generate the same functionbackagainbut multipliedby a constant? The answer is functions of the form exp(rl-r,) since (1.37)

So. we saythat exp(a_r,) is an ei-eenfunction of d ldy and a is the corresponding eigenvalue. As I will discuss theeigenvalues F tell us in moredetailshortly, of theoperator the onlt,valuesofthe physicalpropertycorresponding to the operatorF that can be observed in a laboratorymeasurement. that we encounter SomeF operators possess laboratory eigenvalues that arediscrete or quantized. Forsuchproperties. measurement have will result in only those discretevalues.Other F operators eigenvalues that can take on a continuousrangeof values;for theseproperties, laboratorymeasurement range. can give any value in this continuous


T h eb a s i c s o f q u a n t u mm e c h a n i c s

1 . 2 . 2W a v ef u n c t i o n s
The eigenfunctiono s f a q u a n t u m m e c h a n i c ao l p e r a t o rd e p e n d o n t h e coordinatesupon which the operator acts. The particularoperator that corresponds t o t h e t o t a l e n e r g yo f t h e s y s t e mi s c a l l e dt h e H a m i l t o n i a n operator.The eigenfunctions of this particularoperator are called wave functions. A special case ofan operator corresponding to a phvsicalll,nreasurable quantitv is the HamiltonianoperatorH that relatesto the total enercyof the system. The energyeigenstates ofthe svstemW are functionsofthe coordinates 1g;1 t h a tH d e p e n d s o n a n d o f t i m e l . T h e f u n c t i o ni V ( r 7 ; . 1 ) l l : W - V g i v e st h e probability densitvfor observing the coordinates at the values q; at tirnel. For a manv-particle systemsuchas the H2o molecule" the u'avefunctiondepends o n m a n yc o o r d i n a t e F s .o r H 2 O .i t d e p e n d o s n t h e . x . . r .a . n d : ( o r r . 0 . a n dS 1 coordinates of thetenelectrons andthe.r-. and: (or r. 0. and(t) coordinates oi' .r,. theoxygen nucleus andofthe two protons; a totalof39 coordinates appear in v. ln classical mechanics. the coordinatcs q7 and their correspondins momenta p.i arefunctions of tinre.The state of the system is thendescribed bl,spccifvine q j(l) andp 1(tl.In quantum ntechanics. theconcept that17; is knor,"'n asa funr:tion of tirneis replaced by the concept of the probabilitv dcnsitvfor 1inding Qi ar ? particular "'alue at a particular time lv(r7r. t)lr. Knorvledge of thc corresponding momenta as functions of time is alsorelinquished in quantum nrechanics: lgain. onlyknou'ledge of theprobabilitv densiry for finding7r, r.vith anyparticular r,,aluc at a particular time / remarns. The Hamiltonian eigcnstates are especially irnportant in chenristry because manyof thetoolsthatchemists useto studymolecules probetheenergy states of themolecule. Forexample, nrost spectroscopic methods aredcsigned to deterrnine u,hich energy state a molecule is in. However. thereareotherexperimental melhodsthatmeasure otherproperties (e.g.,the :-cornponent of angular monrentun.r or the total angular momentum). As stated earlier, if the stateof somemolecular svstem is characterized b1'a wavefunctionw that happens to be an eigenfunction of a quanlummechanical operatorF, one can immediatelysay somethingabout what the outcome $,ill be if the physicalproperty F corresponding to the operatorF is measured. In particular, sir.rce Fxt : )",x1.

(r . 3 8 )

wherei 7 is oneof theeigenvalues of F. we know thatthevaluei7 wili be observed if thepropertyF is measured while thernolecule is described by thervave funcrion '4t: .ln fact,oncea measurement of a physicalquantityF hasbeencarried X.i out and a particulareigenvalue ).i hasbeenobservedthe system's rvavefuncrion v becomes the eigenfunction to that eigenvalue. That is, the 1, that corresponds

T h e S c h r o d i n g ee r q u a t i o na n d i t s c o m p o n e n t s


causes the system's wavefunctionto become actof makingthe measurement the of the property that tvasmeasured eigenfunction What happens if someotherpropertyG, r.vhose quantummechanical operator in sucha case? We knou' from what was said earlierthar some is G is measured pr of the operatorGlvill be observed ei_genvaltre in the measurement. But. will wave functionrenrain, the molecr-rlei after G is measured the eigenfunction of F, or will the measurement of G cause V to be altered in a way that makes the stateno longeran eigenfunction molecule's of F? It turns out that if the two F and G obey the condition operators
F G = G F


then.when the propertyG is measured the wavefunction'Q : Xtrvili remain This propertv. unchanged. thattheorderofapplication ofthe two operators does not matter. is calledcontmutation: that is, we savthe tu,ooperators commute if theyobeythispropertv. Let us seehowthisproperty leads to theconclusion about V remaining unchanged if the tr,vo operators comnlute. In particulaq we apply theG operator to the above eigenvalue equation:
C F 7 . ,: G 1 i Xi .

(r . .10)

Next.rveusethe comntutation to re-writcthe leti-hand sideof this equation. and u s et h e f a c tt h a ti , i s a s c a i a n r urnberto t h u so b t a l n

F G7i: r.Q7,


So. nor.v we scc that (G;1,) itself is an ei-uenfunction of F havingeigenvalue ir. So, unlessthereare l.nore than one eigenfirnctions of F corresponding to the eigenr.aluc i; (i.c..unless this cigenvalue is degenerate). GX, n.rust itselfbe proportional to 21r. We write this proportionalirv conclusion as GX,: ltix,. (1.:12)

which meansthat X, is also an eigenfunction of G. This. in turn. meansthat measuring the propertyG rvhilethe systemis described by the wave function tp : t h ew a v et u n c t i o ni:t r e m a i n s X i d o e sn o t c h a n g e X,. So. lvhenthe operators corresponding to two physicalproperties commLlre, once one measures (and tlius causes one of the properties the systemto be an eigenfunction ofthat operator). subsequent measurcment ofthe second operator will (iithe eigenvalue of the first operator is not degenerate) producea uniqtLe eigenvalue ofthe second operator andwill not change the system wavefunction. If the two operators do not commute. one simply can not reachthe above conclusions. In suchcases. measurement of the propertycorresponding to the first operator rvill leadto one ofthe eigenvalues ofthat operator and cause the system lvave function to become the corresponding eigenfunction.However,


T h eb a s i c s of quantum mechanics

subsequent measurement of the secondoperatoru'ill producean eigenvalue of that operator. but the systemu'avefunction will be changed to beconre an crgenfunctionofthe second operator and thusno longerthe eigenfunction ofthe first.

1.2.3 T h eS c h r o d i n g e erq u a t i o n
T h i s e q u a t i o ni s a n e i g e n v a l u e e q u a t i o nf o r t h e e n e r g yo r H a m i l t o n i a n operator;its eigenvaluesprovide the only allowed energy levels of the sysrem.

The ti me-depe n dent eq u ati o n lfthe Hamiltonian operator contains thetimevariable e x p l i c i t l yo ,ne must solvethe time-dependent Schrodingerequation. "means". Beforemovingdeeper into understanding whatquantum mechanics it is useful to learn horv the wave functions V are found by applying the basic equation of quantun.r mechanics. the Schrodinger equation. to a few exactly "easy" soluble modelproblems. Knorvingthe solutions to these vet chernically very relevant modelsr.l,ill then facilitatelearninsmore of the detailsaboutthe structure of quantum mechanics. The Schrodinger equation is a differential equation depending on tirneandon all ofthe spatial coordinates necessarl,to describe rhesystem at hand(thirt1,-nine for the H2O examplecited above).lt is usuallyn,ritten H t U : i 7 16 r y 1 ' 6 , . (1.43)

wherev(qi, t.) is the unknownwave function and H is the operatorcorresponding to the total energyof the system.This operatoris called tl.reHar.niltonian and is formed, as statedabove,by first writing down the classicalmechanical expression for the total energy(kinetic plus potential)in Cartesian coordinates and momenta and then replacingall classicalmomentap; by their quantum mechanical operators p j : -ih 0lSq.i. FortheH2o example usedabove, theclassical mechanical energy of all thirteen particlesis
F _

+ l r ^ - 't - /_J t.t.t ? ,," Z'Zr'i I - f p j -r-r ' -r 'ir- \? ruh +lr*




( r.44)

wherethe indicesi andj are usedto label the l0 electrons whose30 Cartesian coordinates arelq il anda and b labelthe threenucleiu,hose charges aredenoted {Zo}, and whosenine cartesiancoordinatesare lqo}. The electronand nuclear

T h e S c h r o d i n g ee r q u a t i o na n d i t s c o m p o n e n t s


are denotedrr. and {n,,}, respectively. masses The corresponding Hamiltonian is operator

H=E l .:l*-+Tl *#
.+[-*#.:+'#l .'15)
NoticethatH is a second orderdifferential operator in thespace ofthe 39 Cartesian that describe coordinates the positionsofrhe ren electrons and is a second order operator because the momentaappearin the kinetic energyas pr2 p;,and the quantummechanical and operator for eachmomentump : _ f ttlI 0q is of first order.TheSchrodingerequationfor the H2o example at hand then reads:


- 1\- "' - \- Z,e:w l-Ai2n,dq;

1 ??r,, a: ?,.," -tl_ l

* 1 l Z , Z n e :\ y
2? rr.h

;l r! lnAt

( 1.16)

The Hamiltonianin this casecontains / nowhere. An exampleof a casewhere11 doescontain / occurs whenan oscillating electric field E cos(ror) alongthe-r-axrs interacts with the electrons and nuclei and a term ) Z,rX,,f.cos((r/ )- f e;r7E cos(rr-rr) (1.47)

is addedto the Hamiltonian.Here,xo and.,vi denotethe.r coordinates of the ath nucleus and the7th electron. respectivelv. The ti me-i ndepe ndent eq uatio n lf the Hamiltonianoperator does not containthe time variableexplicitly, one can solve the time-independent Schrodingerequation. In cases wherethe classicalenergy, and hencethe quantumHamiltonian,do not contarn termsthatareexplicitlyrimedependent (e.g..interactions with time varying externalelectric or magneticfields rvould add to the above classical energyexpression time dependent terms),the separations of variables techniques can be usedto reducethe Schrodinger equationto a time-independent equation. In suchcases, H is not explicitlytime dependent, so one can assume that v (.q i ' t ) is of the form (n.b.,this stepis an exampleof the useof the separations of variables methodto solvea differentialequation)
V ( q , ,t ) = W ( q i)F(t) (l.4E)


T h e b a s i c so f q u a n t u mm e c h a n i c s

gives Substituting this "ansatz"into the equation Schrodin_ser

V ( q 1 )i t t 0 F l ' d t: F Q ) H V ( qt t . (1.49)

D i v i d i n gb y V ( q 1 1 F ( tt)h e ng i v e s F t t i ht ) F l i t r t : W i [ H , ! ( 4)i] . (1.50)

SinceF(l ) is only a functionof time t. andtU(q 1)is only a functionof the spatial coordinates and riglit-hand sidesmust be equal the left-hand lq 1], andbecause for all valuesof t and of lq il, both the left- and right-hand sidesmust equala thatareernbodied constant. lf this constant in this is calledE. the two equations separated Schrodinger equationreadas follou,s:
HV(q,): EV(q,). ifidF(t)ldt: EF(t). ( l . 5 l)

Thefirstofthese equations is called thetin-re-independent Sclrrodinger equatron: it is a so-called eigenr,alue equation in u'hichoneis asked to find functions that1,ield multipleof ther.nselves a constant when actedon by the Hamillonian operator. Suchfunctions arecalled eigenfunctions ofH andthecorresponding coustallts are called c i g . e n r a l uo ef sH . F o re x a m p l e i. f H u e r eo f ' r h e f o r m ( _ l i ' 2 . \ lt ; t :, d Q : H" tlrenfunctions of thc form exp(inrQ) would be eigenfunctions because I li d: I ln:h:l ,' l e x p ( i , , i @ ) : l * f crptiirrd,). ztra6,1 ll.-i.l)


In thiscase. rr 2tt2 In thisexample. theHarriltonian contains 12tvtis theeigenvalue. the squareof an angularmomentumoperator(recall earlierthat u,'eshou'ed tlre :-cornponent of angular momentum is to equal-ih d ldQ). \Vhen the Schrcidingerequation can be separatedto -senerate a timeindependent equation the spatial describing coordinate dependence ofthe u'ave function, the ei_eenvalue E mustbe retumed to the equation F(t) to determining part of the wavefunction.By solving find the time-dependent
ifldF(r)ldt: EF(t)


once E is known.oneobtains
F(t) = gapl-i E1171,


and the full wave function can be written as v ( qi . r ) : w ( q i ) exp(i Et ltt). For the aboveexample, the time dependence is erpressed by F(r) : exp(-irlnt2ti 1zll1itt1. (1.56)

(l . s 7 )

T h e S c h r o d i n g ee r q u a t i o na n d i t s c o m p o n e n r s


wheneverthe Hamiltoniandoes not dependon time explicitly, In summary, one can solvethe time-independent Schrodinger equation first and thenobtain as exp(-i El/fi) oncethe energyE is known. In the case rhetime dependence of rnolecularstructuretheory,it is a quite dauntingtask even to approximately equation soivethe full Schrodinger because it is a partialdifferential equarion on all of the coordinates depending of the electrons and nucleiin the molecule. For this reason.there are various approximations that one usually implements to study molecularstructurer.rsing when attempting quantummechanics. The Born-O ppen hei me r approxi m ati on one of the mostimportantapproximations relatingto applyingquantummechanis knownas the Born-oppenheimer ics to molecules (Bo) approximation. The this approximation basicideabehind realizing thatin the full electronsplus-nuclei Hamiltonian operator introduced above,

' -- l \ - - " ' - ' t a l H : t l - , iz n tr itq: 2?'',,


(r . 5 8 )



7 7 . : z!/ zxc t'u.h

2nr,,;)q,] 2

the tirne scales ivith which the electrons and nuclei move are generally quite difl'erent. In particular. the heavynuclei(i.e.,evena H nucleus weighsnearly 2000timeswhatan electron weighs)move(i.e.,vibrateandrotate) moreslowly thando the lirrhter electrons. Thus.r','c expect the electrons to be ableto ..adjust,' theirmotions to themuchrrrore slowlymo'n,ing nuclei.Thisobservation motivates to solvethe Schrcidinger equation tbr the movement of the electrons in the presence of fixed nuclei as a vvilvro represent the fully adjusted srateof the electrons at any fixedpositions ofthe nuclei. The electronic Hamiltonian thatpertains to the motions of theelectrons in the presence of so-called clarnped nuclei.

- * 1 t ' ' ' - r'Z{ l H : -\ - l - l 'r tit , " t/ :t,1: )L,".,


,,, l'


produces as its eigenvalues. throughthe equation

HO1(q , q,). 1 i r l , ) : E r k l , , ) , ! . t ( qI


energres ErGl,) that dependon where the nuclei are located(i.e., the {r7,,} coordinates). As its eigenfunctions. one obtains what arecalledelectronic wave functions r7,,)) which also depend ltLrkti I on wherethe nucleiarelocated. The energies E xQ") arewhatwe usually call potential energy surfaces. An example of sucha surlace is shoivnin Fig. 1.5.This surface depends on two geometrical coordinates a'd is a plot of one particular {r7,,} eigenvalue EL@,) vs. these two coordinates.


T h e b a s i c so f q u a n t u mm e c h a n i c s

Secondorder saddlePotnl A fransrtion structure

Minimum for product A

- 0.,5 Two-dimensional potentialenergysurface s h o w i n gl o c a lm i n i m a , transitionstatesand p a t h sc o n n e c t i n g them.

Secondorder n saddlepoint

Minimum for reactant

\ralley-ridgc potnt inflection

Although this plot has more information on it than we shall discussnou'. to be tlireeminima (i.e..points are worth noting.Thereappear a few features vanishand u'here of -87 rvith respectto both coordinates r,l,here the derir"atives as we u'ill seetoThesepoints correspond" the surfacehas positivecurvature). u,ard the end of this introductorymaterial,to geometriesof stablet.nolecular The surfacealso displaystwo first order saddlepoints (labeledtranstructures. A and B) that connectthe threemininra.Thesepointshavezero sition structures but have one direction first derivativeof E.r with respectto both coordinates of negativecurvature.As we will show later, these points describetransition that play crucial roles in the kineticsof transitionsamongthe three stable states geometries. eachmolecule just one of the tJ surfaces; Keep in mind that Fig. 1.5shows as well as an surface(i.e., the one that is lowest in energ.v) has a ground-state ofthe discussion to our nou'return Let's surfaces. infinitenumberofexcited-state in hand. surface energy an such has one BO model and ask what one doesonce within the^Bo model. asThe motions of the nuclei are subsequently, equationin u'hich L"{-(h'l2nt,,)d!l\q;-l sumed to obey a Schrodinger for the a rotation-vibrationHarniltonian defines E ro.6] * 1l2l,n ZoZ6e2 r@) f and energies I'ibrational and The rotational particularenergystateE5 ofinterest. the inof value (i.e., each for wave functionsbelongingto eachelectronicstate such a rvith equation dex K in E x@)) arethen found by solving a Schrodinger Hamiltonian. This BO model forms the basis of much of how chemistsview tnolecular as appliedto forrraldehyde For exarnple, structureand rnolecularspectroscopy. spin H2C:O, we speakof the singletgroundelectronicstate(with all electrons as states its vibrational and orbitals) energy the lowest occupying paired and

M o t i o no f a p a r t i c l e in onedimension


states and their vibrational nell as the n --+ z* and ir --->lr*electronic levels. later in this text. the Althoughmuch more will be said about theseconcepts of the conceptsof electronicenergysurfaces (i.e.. the studentshould be arvare the vibration-rotarion and states thatbelongro eachsuchsurface. lExe,)]) Having been introducedto the conceptsof operators,wave functions.the andits schrodin-eer equation, it is important Hamiltonian to now consider several of the applications of these concepts. The examples examples treated belorvwere to providethereader with vaiuable chosen experience in solvingtheSchrodinger they werealsochosen because they form the n]ostelementary equation: chemical of electronic motionsin conjugated models molecules and in atoms, rotations of and vibrations linearmolecules, of chemical bonds.

- motion 1.3 Yourfirst applicationof quantum mechanics of a particlein one dimension

This is a very important problem whose solutionschemistsuse to model a wide variety of phenomena. Let's begin by examining the motion of a singleparticleof mass,n ln one direction which rvewill call "r rvhiler-rnder the influence of a potential denoterl Z(,r). The classical expression for the total energyof such a systemis .E : p212n -t V(x), rvhere p is the momentum of the particlealong ther-axis. To focuson specific examples, consider horvthis particlewould moveif I/(.r.1 il'ere of the forms in Fig. I .6. wherethe total energyE is denoted by theposition ofthe horizontal line.

1.3.1 plr o b a b i l i td ye n s i t y Classica

I would like you to imaginewhattheprobabilitydensitywould be for this particle moving with total energyE and with I/(,r) varying as the threeplots in Fig. L6

Three potentials characteristic showing left and right classica t lu r n i n gp o i n t s at energiesdenotedby t h e h o r i z o n t aIli n e s .


mechanics of quantum T h eb a s i c s

to havea the particle imagine densitl'. theprobability To conceptualize illustrate. to it andthink of this lampblinkingsay100timesftrreach attached blinkinglan.rp from its lefi turning a full transit to complete for theparticle time intervalit takes and point to its right turning point and back to the former.The turning points,r-s iau's. Ne\\'ton's were mo'"'ing under particle, if it positions the at which -rRarethe These (asthe momentum sign)andturn around. changes direction wouldreverse positionscan be found by askingwherethe momentumgoesto zero: rr . 0: p:(2m(E - I'(.t)) (1.6i)

energvE : as potential appears rvhere all ofthe energy arethe positions These in the abovefiguresto the pointsrvherethe dark horlzontal I/(.x) and correspond plot. in the central linestouchthe I'(r)plots as sho'uvn the fractionof'tirllethe The probabilitydensityat any valueof -r:represents (i.e.. r/.r).Think of forrrling u'ithin.r and,t value this of ..r* particlespends at to the particleto shedlight by allowingthe blinking lantpattachcd this density' o1to tliis light for many oscillations plate that is exposed on a photo-eraphic this probability one can express -r1 and;rp. Alternatively. the particlebet\\'een r/.r" by thevelocitl'of theparticle distance P(r) by dividingthe spatial amplitude at tlie nointr:
I r r r rr i r P ( - t ): ( 2 m ( E - I " ( . r )) (i.62)

motion.P(,t)tl'ill be smallat,t the particle's throughout E is constant Because 'ui'here (i.e.. l/ is lou') andri'ill be high quickly particle is mo'u'ing the valuesu,here plate tr/is high). So. the photographic wherethe particlemovesslowly 1r,r,here the particlemovesslou'lyin u'ill shou, a brightregionwhere I/ is high (because where tr' is lou'. suchregions)and lessbrightness the by analyzing probability anticipated that the densities line is The bottom histogran.r appear asthe dynamics of this oneparticle'uvould Newtonian classical (and hashighkineticenergy Wheretheparticle plotsshownin Fig. 1.7 illustrate. moves time and P(.t) is small.Wheretheparticle it spends less thuslower Z(.lr)),

Classical ty plotsfor the three potentials shown i n F i g .1 . 6 .

M o t i o no f a p a r t i c l e in one dimension

23 spendsmore time and P(.r) is larger.For the plot on the ri_eht, /(,r) within the "box". so the speed is constant. is constant hencep(.r) is constant rvithinthis one-dimensional all .v values box. I ask that you keepthese fLrr piots they are very difrerentfrom what one finds when one solves in nrind because equation for this sameproblem. the Schrcidinger Also please keepin mind that represent plots what one expectsif the particle were moving according these to Newtonian (w,hich dynamics we know it is notl). classical

treatment 1 . 3 . 2O u a n t u m
To solve tbr the quantLlm mechanical wavefunctionsand energies of this same we first problem, write the Hamiltonianoperator as discussed aboveby replacing
n Ov -lll(l /Ll.\".

h' ,t: Il:-'--l+l'rrr

lilt tl.\-


We then try to find solutions ry'(.r) to Hrlr : ErL that obey certainconditions. Theseconditions are related ro the fact that iry'(.r)12 is supposed to be the probability densityfbr findinethe particlebetrveen -r and.r * r/.r.To keepthingsas simpleas possible, let'sfocuson the "box" potential/ shorvn in the right side of Fig.1.7. T h i sp o t e n t i a l . x p r e s s ea e dsa f u n c t i o n of ,r is: V(x\: cc for-r < 0 : 0 fbr.r-between andfbr,r > L: I/1.r1 0 and l. The factthat tr/is infinitefor-r < 0 andfor.r > l. andthatthe totalenergy E mustbe finite.salts that /r mustvanish in these : two regions 0 for_r < 0 and dt forx > l). This conditionmeans that the particlecan not access thesereslons wherethe potential is infinite.Thc second condition that.nve makeuseof is that thisrrreans thatrheprobability /(-t ) mustbe continuous: of theparticle beingrt,r cannot be discontinuously related to theprobability ofit beingat a nearby pornr.

1 . 3 . 3E n e r g i e s andwavefunctions
The second orderdift-erential equation
il tlllr -;-. -t tr/\r)tlr : Etlt ^



hastwo solutions (becar.rse it is a second orderequation) in the regionbetrveen "r:0andx:L: ' c o s ( , t - r ) . r v h e r e A i s d e f i n e dk / :sin(l.r) and ry: a: s( 2 m E l t t : 1 | i 1 . ( 1 . 6 5 ) Hence. the mostgeneral solutionis somecombination of these trvo: ty': .1sintA.r) + B cosrfr.r'.y.


Thebasics o f q u a n t u mm e c h a n i c s

T h e f a c t t h a t r y ' m u s t v a n i s h a t , v : 0 t n . b . . r / r v a n i s h e s< f o0 rx andiscontinuous. so it mustr.'anish at tlrepoint.r :0)means that the rveithtinganrplitude of the cos(Ax)term mustr,'anish because cos(Ar): I at-t : 0. That is. B =0. (1.67)

The amplitude of the sin(rt,r) rerm is not affecred by the condition that {r vanish ot.r : 0. sincesin(t.r) itselfr.anishes at,r : 0. So.nou,weknou,that{r is really of the forn:
/(.r):.{ sin(tr-). (1.6[i)

The condition that 1/r alsovanishat -v : I hastrvopossible implications. Either . 4 : 0 o r f r m u s tb e s u c ht h a t s i n ( A l ) : 0 . T h e o p t i o nI : 0 w o u l dl e a dt o an answer ry'that vanishes at all values of -r and thusa probability that vanishes everywhere. This is unacceptable because it rvouidimplv thattheparticle is never observed anywhere. The otherpossibility is that sin(ft1): 0. Let'sexplore this ansrver because rt offers the first exanrpleof energyquantization that you have probablyencountered. As you know.the sinefunctionvanishes at integral multiples of :r. Hence AL mustbe somemultipleof :r: let'scall the integer : n andu'riteZA rz (using the definitionof fr) in the form:
Lt}nEllitt): nn. Solving this equation for the energy f , we obtain:


E : n1r2rt l(2mt).

(r . 7 0 )

This result saysthat the only energyvaluesthat are capableof grving a wave function ry'(x)that will obey the aboveconditionsare thesespecificE r.alues. In otherwords,not all energyvaiuesare"allowed"in the sense thattheycanproduce ry'functionsthat are continuousand vanishin regionswhere z(x) is infinite. If one usesan energyE that is not one ofthe allowedvaluesand substitutes this E into sin(*;r),the resultant functionwill not r,anish at x : L.I hopethe solutionto this problemremindsyou of the violin stringthatwe discussed earlier. Recallthat the violin stringbeing tied down at x : 0 and at -r : z gaverise to quantization just asthe conditionsthat ry'be continuous of the wavelength at;r-: 0 ar.rd x : Z gaveenergyquantization. Substituting k : nn /L into ry': I sin(k,r)gives
VQ)= Asin(nrx/L)


The valueof I can be found by remembering that lq/ l2 is supposed to represent theprobabilitydensityfor finding the particleat x. Suchprobabilitydensities are

M o t i o no f a p a r t i c l e in one dimension


to be normalized. rneaningthat their integralover all x valuesshould supposed amountto unity. So, we can find I by requiringthat
f r


: l . -1 zI L ) t t x . llttr )li,/.t t : s i n 2 t rx J ;l


where the integral rangesfrom r : 0 to x : L. Looking up the integral of sin:(a,rI and solving the aboveequationfor the so-called normalizationconsranr I gtves A : (2lDtt2 andso rt sin(nr x I L) /(-r) : (2111t (1.73)

(r . 7 4 )

Thevaluesthatn cantakeon aren : l, 2. 3. . . .; the choiceie : 0 is unaccentable it would producea wavefunction ry'(.t)that vanishes because at all r. The full ,r- and t-dependent wavefunctionsare then given as

v(,r.r):(:)'rin''l'r ' .rl-.t'::'!l

\ L / L L lttl L-/lt )


Noticethatthe spatial probability density is not depenclent on timeand lv1,r. r)12 is equalto lry'(.r)12 because the complexexponential disappears when v*w is formed.This means rhatthe probability of findingthe particleat various values of "r is time-independent. Anotherthing I wantvou to noticeis that,unlikethe classical dynamics case. notall energy values E areallor.ved. In theNewtonian dynamics situation, E could be specified andthe particie's momentum at any-r valuewas thendetermined to within a sign.In contrast. in quantum mechanics onemustdetermine, by solving the Schrcidinger equation.rvhatthe allowedl'aluesof 6 are. TheseE values are quantized meaning thattheyoccuronly for discrete values .t : ,2 r2h) /(2r, L2) determined bv a quantum numberrr. by the mass of the particlem, andbycharacteristics ofthe potential this case).

1 . 3 . 4P r o b a b i l i t y densities
Let's now look at sorne of the wave functionsv(.r) and compare the probability densities to the classical probabilitydensities lv(.r)ir that they represent discussed earlier.The n : 1 and n : 2 wave functions are shown in the top of Fig. 1.8.The corresponding probabilit-v densities are shownbelowthe wave functionsin two tbrmats (as n--vplots and shaded plots that could relateto the flashing light way of monitoring theparticle's location thatu'e discussed earlier). A more completesetof r.vave functions(for izrangingfrom 1 to 7) are shownin F i e .1 . 9 .


T h e b a s i c so f o u a n t u mm e c h a n i c s


The two lowest wave functions and probability densities.





Seven lowestwave functions andenergies.

Motionof a particle in one dimension


numbern increases, Noticethat as the quantum the energyE also increases rvith n in this case) andthe numberof nodesin v also increases. lquadratically Also notice that the probability densitiesare very different from what we enearlierfor theclassical case. Fo[ example. countered look at ther : I andil : 2 and compare them to the classical densities densityillustrated in Fig. 1.10. The densityis easyto understand classical because we arefamiliarwith classical dyIn this case, we saythat P(.r) is constant namics. within the box because the fact (.r) is constant causes rhekineticenergy that tr/ andhence the speed ofthe particle In contrast. to remainconstant. the r : I quantumu'avelirnction'sp(.r) plot is in the rniddleof the box and falls to zeroat the walls.The n :2 density peaked hastwo peaksP(-r) (oneto the leti of the box midpoint.and one to the right).a C l a s s i cIa nodeat the box midpoint.and falls to zeroat the thing that students p r o b a b i l i t y d e n s i t yf o r "how oftenaskme is doesthe particle gerfrom beingin the lefi peakto beingin p o t e n t i a l s h o w n . theright peakif it haszerochance of everbein_q at the midpointwherethenode is?"The difficr"rlty rviththis question is rhatit is posedin a terminology tharasks for a classical dynamics answer. asking"horvdoestheparticle get. . ." one is dernanding an answer that involves describing its motion ( moves from hereat time t1 to thereat time 11). Unfortunatell,. quantum mechanics does notdealwith issues suchasa particle's (i.e..rvhere trajectory it is at various tinres) butonly vu'ith its probabilty of beingsomewhere (i.e.,lw l:;. The nc'xt section will treatsuchparadoxical issues evenfirrther.

1.3.5 Classica aln d q u a n t u mp r o b a b i l i t d yensities

As.lustnoted, it is temptingfor mostbeginning students of quanturn mechanics to attemptto lnterpretthe qr-rantum behaviorof a particlein classical terms. However. this adventure is tull of daneerand boundto fail becar-rse srnall.light particles simply do not moveaccording to Nervton's larvs. To illustrate. lets try to "undersrand" r'"'hat kind of (classical) motion wor-rld be consistenr lvith the ri : I or n :2 quanturn P(_r)plotsshownin Fig. 1.8.However. as I hope1,ou anticipate. thisattcrnpt at gaining classical understanding of a quantum result rvill not "work" in that it r'"'ill leadto nonsensical results. My point in leading you ro attempt sucha classical understanding is to teachyou thatclassical andquantum results aresimplydifferent andthatyou mustresist theurgeto impose a classical understanding on quantum results. For the zr: I case,we note that P(x) is highestat the box midpoint and vanishes at.r : 0 and,r : L. Lna classical mechanics worlcl this would mean that the particle movesslowly near-y : L/2 andmore quickly near-r : 0 and r : L. Because the particle'stotai energyE must remain constantas it moves. in regions where it moves slowlv. the potential it experiences must be high. and where it moves quickly, tr/ must be small. This analysis (n.b., basedon classical concepts) would leadus to conclude that the n : I p(i arisesfrom tne


The basics o f q u a n t u mm e c h a n i c s

particlemoving in a potentialthat is high near.r : L /2 anrlloll, as-r:approaches 0orZ. A similaranalysis of the n :2 P(x) plot would leadus to conclude thatthe particlefor which this is the correctp(_r) rnustexperience potential a that is high midwaybetween:r: 0 and x : L/2,high midu,ayberu,een .r : L 12 and x = L , a n d v e r y l o w n e a r x: L / 2 a n d n e a r - r: 0 a n d r : r . T h e s e c o n c l u s i o n s are"crazy"because n'e know that the potentialt,(-r)for which we solvedthe Schrodin-eer equation ro generate bothof thewavefunoions (andbothprobability densities) is constant between -r : 0 andt : L. That is. ."ve know the samel,(-r ) applies to theparticle movingin thell : I andr : 2 states. whereas theclassical motion analysis offeredabovesuggests that l,(l ) is differentfor thesetwo cases. what is wron-q rvith our attemptto understand the quantump(.r) prots?The mistake we madewas in attempting to apprythe equatio'sandconcepts of classicaldynarnics to a P(.i-)protthat did not arisefrom classicar motion.Siniply put' one can not ask how the particleis mo'ing (i.e..what is its speed at variouspositions) whentheparticle is undergoing quantum dynamics. Most students. r,r'hen first experiencing quantumrvave functionsandquantum probabilities, trv to thinkof theparticle movingin a classical way thatis consistenl with thequantum P(-r). This attempt to retaina degree of classical understanding of theparticle's movement is alwaysrnetwith frustration,as I illustratedu,ith the aboveexamole andwill illustrate laterin othercases. continuingwith thisfirstexarnple of hou'onesolves theSchrodinger equatlon and how one thinks of the quantized E 'alues and u,avefunctionsv, let me offer a little more optimisticnote than offeredin the precedingdiscussion. If we examine the w(.-v) plot shown in Fig. 1.9fern :7, andthi'k orthe corresponding P(;r) : lv(x)12,we notethatthe p(.r-) plot rvould look something like thatshown in Fig. 1.11.It would haveseven maximaseparated by six nodes. If we wereto prot
I 0.9 0.8 0.7
^. 5 r! (\A 0.5 I I


\ I

iI 1 I

V o.c
0.3 0.2
Ouantum probabilitydensityfor n : 7 s h o w i n gs e v e n peaksand six nodes.

0.1 I 0




M o t i o no f a p a r t i c l e in one dimension


V (.r) lr for a very larger valuesuchasn : 55,we would find a P(,r) plot having 1 by 54 nodes,with the maxima separated approximately 55 maxima separated os f ( 1 / 5 5 I ) . S u c ha p l o t ,w h e nv i e w e di n a " c o a r s e grained" sense b),distance with somewhat blurred vision positions on the and heights focusinu of 1i.e.. very looks much like the classical P(,r)plot in which P(.r) is the maxima) -r. In fact, general it is a for all resultof quantummechanics that the constant quanfumPt.r) distributionsfbr largequantumnumberstake on the form of the P(-r) for the samepotentialZ that was usedto solvethe Schrodinger classical equation.It is also true that classicaland quantum results agree when one is with heavyparticles. Forexample, a givenparticle-in-a-box energv Cn : dealing for a heavier particleat highern-values thanfor n:h: I \2ntL2) u,ouldbe achieved heavier particles, movingwith a givenenergyE. have a lighterpalticle.Hence, probability r and thusmoreclassical distributions. higher thisso-called quantum-classical \!'e rvill encounter principle correspondence 'nve examineother model problems.It is an important property of again "r,'hen to the Schrodinger equation because it is what allowsus to bridgethe solutions "gap" betrveen usingthe Schrodinger equation to trearsmall,light particles and (big, heavy)systems. for macroscopic theNewtonequations Anotherthing I u'ould like you to be arvare of concerning the solutions ry' and .E to this Schrodinger equation is that eachpair of wavc functionsry',, and r/r,,belonging to difl-erent qltantum numbers n andn'(and to different ener_qiesl a prope rt,vterrned display orthonormality. This propertymeans that not only are tfr,,and, {r,, eachnormalized
r t


ltrlt,,:,/t:/ .a,,:lt'.
, J


but they are also orthogonal to eachother

o= lr',t,,,r',t,,, a,


where the complex conjugate* of the first function appearsonly when the ry' (you haveonly seenone suchcase solutions containimaginary components thus far - the exp(ill @ of the:-component of an-qular momentum). It ) eigentunctions is commonto write the integrals the normalization displaying and orthogonality conditions in the fbllorvine Diracnotation: so-called
| - / r l r ,|, 1 1 , , \ 0: 1 r l t , ,r' ! , , ) .


where the l) and (l si'mbolsrepresent tb and lt*, respectively, and putting the two together in the (l) construct impliesthe integration overthevariable thatry' depends upon. The orthogonality condition canbe viewedas similarto the condition of two vectorsv1 and v2 beingperpendicular. in which casetheir scalar(sometirnes "dot") product called vanishes Vl . vr : 0. I wantyou to keepthisproperty in mind


Thebasics o f q u a n t u mm e c h a n i c s

particle-innot only of these you r.l'illsoonseethat it is a characteristic because Schrodinger from any obtained functions w,ar.,e a-box wave functionsbut of all equatlon. In fact, the orthogonalityproperty is evenbroaderthan the abovediscusston forrnedas discussed operators It turnsout that all quantummechanical suggests. -ihd ldq operator p the corresponding by (replacing momenta Cartesian earlier to be so-called shor'vn can be as thev are) coordinates all Cartesian and leat'ing u'henthey that they form Hermitianmatrices This rneans Hermitianoperators. are integratedover. are placed betweenpairs of functionsand the coordinates vu'hen acting on a set of F an operator of representation the rnatrix For example, denoted functions {dr} is

: Lt *;rr' u, F rL : ( Q t t F t Q |

(1 . 7 e )

formed following the rules finds that For all of the operators property: following the have matrices these
r / t . rr J _I -r +


rvhichmakesthe matricesu'hat we call Hermitian.lf tlre functionsupon u'hich turn parts(i.e..arereal).thenthe tnatrices F actsand F itseifhaveno imaginary out to be svmmetric:
F r . L: Ft.r

(r . 8) l

The importanceof the Hermiticity oI symlnetryof thesematriceslies in the fact eigenvalues haveall real(i.e.,not cor.t.rpler) tl.rat it canbe shownthat suchmatrices that are orthogonal. and haveeigenvectors not just the Hamiltonian,have real So, all quantummechanicaloperators, in are rvhat can be measured (this is good since theseeigenvalues eigenvalues eigenfunctions. of that property) and ortho-qonal observation any experimental we make use of them many It is importantto keep thesefacts in mind because times throughoutthis text.

o f w a v ef u n c t i o n s 1 . 3 . 6T i m e p r o p a g a t i o n
V(x) : (2lL)t12 sn(nitx lL) havingan For a systemthat existsin an eigenstate u'avefunctionis energyEn : n2r2h2 lQmLz),the time-dependent

: (?)"',inff*r v(x. r) (-?),


which can be generated by applying the so-called time evolution operator U(l' 0) to the wave function at I : 0:

0)v(,r,0) V(x.r) : U(r,

(1 . 8 3 )

M o t i o no f a p a r t i c l e in one dimension

an explicitform for U(t, t') is rvhere

L ( r .r ' \ : . * o[ - " ' L

*'''"-l. n l


densitythat doesnot depend functionV(.r, t) has a spatialprobability on Thctimebecause

: (;) ""' (?) v.(.r. r)v(.r.,,

(1 . 8 5 )

sinceexp(-rtE,'l/i) exp(itE,, l/i) : l. However it is possibleto preparesystems in states that are not singleeigenstates; (evenin real laboratorysettings) we call superposition states. For example, consider a particlemovingalong suchstates within the "box" potentialbut in a statewhosewave function at some the-r--axis initialtime/:0is


, / l \ l :

/ 1 7 r \

. . r 2 t l :

/ l - z . r ' \

. )-,,(;),'"(?)


a:n d z : 2 e i g e n s t a t e s . T h e p r o b a b i l i t v d e n s i t y T h i s i s a s r - r p e r p o s i t i o n o f t h eIn ndi t h t h i s f u n c t i o n is associate

: I ;,'",(?) +/ sin: r,r,r' (?) - r(?) |

' t ' n /(
lrr\ / 1 . - r .tr I

r /t'"( . ,/i


Then : I andn : 2 components, the superposition V. andthe probability den: sityat 1 0l V lr areshownin thefirstthreepanels of Fig. l. 12. It should be noted that the probability densityassociared with this superposition srateis not symmetricaboutthe"r : I/2 rnidpointeven though then : I andn : 2 component wavefunctions and densities are.Sucha densitydescribes the particlelocalized more stronglyin the large-"v regionof the box than in the small-,rregion. Now. let's considerthe superposition wave function and its densitl,at later times. Applying the time evolutionoperator exp(-itHl/i) to V(r,0) generates thistime-evolved tunctionat time /:

v(; rr 1* : '(-#)



' ( ; )" ' ' ( ? ) ' - io )( -''


",'" ' { i ) ' , , " ( T ) - ' ' '(?r) (?)l



The spatialprobabilitydensityassociated with this W is

,)r:: j{(;),'",(+) . (;),,'',(?) rv(r -'(?).o, - u,)if,', (+),'"(?)] o8e) [ru,


T h eb a s i c s o f q u a n t u mm e c h a n i c s

I d o.E

E t,.o
l i . . -

/ i I

r I--r\
\ \
f_' .l

u.l 0 ^ 06 0.i 04




^ _0.1


(1.-l ()l

/ l






! 7


0 ( 1I.



^l t.l f




{ \


.\ .= :

0 N




a |I,


L_] -

jflff r h e n : 1 a n d n : 2 w a v e f u n c t i o n st,h e i r superposition a,n d t h e a n dt i m e - e v o l v ep dr o b a b i l i t y densities of thesuperposition.

At r : 0' this functionclearlyreduces to thatu,ritten earlierfor v(r.0). Notice thatastimeevorves. thisdensity changes because of thecos[(82- E 1ltf til factor it contains'In particular,note that as r moves through a period of rength6l : n h/ ( E 2 - f r ). the cosfactorcha'gessign. Thatis. for r : 0. the cosfactoris + l ; f o r l : r / i / ( E 2 - t r ) , t h ec o sf a c t o r i s_ l ; f o r : 2 r / i l ( E z _ t Er ).itreturns to * L The resultof this time variationin the cosfactor is that lV l: .lrun-c.,in forn.r from that shownin the bottom left paner of Fig. l .12 to tr-ratshou,n in the bottom right panel (at t : trril(E2 - 6r)) and then back to the fbr'i in the bottom reft panel(at t : 2tr11/(Ez - E t)). one caninterpret thistime variation asdescribing the particlekprobabilitydensity(not its classicar positionl),initiaily Iocalized toward the right side of the box, moving to the left and then back to the rr_qht. of course, this time evolution will continue overmore and more cycres as trnre evolves. This exampleiilustratesonce againthe difficulty with attemptingto locarize particles tliat arebeingdescribed by quantum wave-functions. For exampre. a particle that is characterized by the eigenstate (2/ D) /2 sin(tr x I L) i, rn"rill*.,u ," be detected fleor'i : L/2thannearir :0 orrj r because the square of this functionislargenear =- rL / 2 . A p a r t i c l e i n t h e s t a t (e 2lDt/2rin1:n..7tj,smort likelizto b e f o u n d r & r x: L / 4 a n d x : 3Lf4,butnotnear,r : 0,x :

M o t i o no f a p a r t i c l e in one dimension


.r = L. The issueof horv the particle in the latter statemovesfrom being near quantummechanics dealsrvith.euanfum r = L f 4 to x : 3 L l4 is not something not allow us does to follow particle's the trajectory. which is what we mechanics Nevertheless. needto know whenwe askhow it movesfrom oneplaceto another. wavefunctionscan offer"to someextent,the opportunityto tbllow superposition statewritten aboveas the motionof the particle.For example,the superposition 2 t / 2 Q l L ) t / 2 s i n ( 2 n x l L ) h a saprobabilityamplis i n ( l z r l Z ) 2-r,:12111112 with time changes as shown in the figure. Moreover,this amplitude's tude that major peakdoesmove from side to side within the box as time evolves.So, in we ciln say with what frequencythe major peakmovesback and forth. this case. this allor.vs us to "follorv" the particle'smovements. In a sense. but only to the are that'"ve satisfied with ascribingits locationto the positionof the major extent peakin its probabilitydistribution.That is, we can not really foilor.v its "precise" location.but we can follor,vthe location of where it is very likely to be found. This is an importantobservation that I hopethe student will keepfreshin mind. It is alsoan importantingredientin modernquantumdynamicsin which localized wavepackets, similarto superposed eigenstates, are usedto detailthe position of a particle's andspeed main probability peak. density Thcaboveexampleillustrates how one time-evolves a \ryave functiontharcan be expressed as a linearcombination (i.e..superposition) of eigensrates of the problem at hand. There is a large amount of current eftbrt in the theoretical chemistry communityaimedat developing elicient approximations to the exp(-i t H lll) evolution operator thatdo not requireV(.r. 0) to be explicitl_y rvrittenasa sumof eigenstates. This is important because, for mostsystems of direct relevance to molecules, one can not solvefor the eigenstates; it is simply too difficult to do so. You can find a significantlymore detailedtreatmentof this subject at the research-level in my TheoryPage web siteand my el,tIC tertbook. However. let'sspenda little time on a brief introductionto what is involved. The problemis ro express exp(-itHlh)V(qr), whereV(qr) is some initial wave function but not an eigenstate, in a manner that does not require one to first find the eigenstates {V7} of H and to expand V in terms of these eigenstates:


( 1.e0)

afterwhich the desiredftlnction is written as

: "t (-#) v@,) 1,,*,*,(-+)


The basicideais to breakH into its kinetic I andpotentialtr/energycomponents and to realizethat the differentialoperatorsappearin I only. The importance of this observation lies in the fact that I and Z do not commute,which means thaLTV is not equal to ZI (n.b.,for two quantities to commutemeansthat their


The basics o f q u a n t u mm e c h a n i c s

order of appearance does not t.natter). Why do they not conrmute'lBecauseI second contains derivatives n'ithrespect tothecoordinates on, {q , } that I' depends so.for example, d2I d q2LI,@)V (q )l is not equalto Il (q ) d2i d (12V (r7 ). The fact that r and l' do not commuteis inrportant because the rnostcommon approach to approxrmating exp(-rlH/fi) is to rvritethis singleexpor.rential in rerms of exp(-itTlh) and exp(-lri.'/fi). However. the identity

:*'(-+) *'(-f) *'(-f)

(l q2)

is not fully valid as one can seeby expanding all threeofthe aboveexponential factors a s e x p ( . r ) : I * . r - + x 2 / 2 ! * . . . . a n d n o r i n _tq h a l t h e r $ , os i d e so f t h c above equation only a-eree if one canassulne thatTl': I'L u, rvenotedis not true. In mostr.nodern approaches to time propagation. onedividesthe time interval r into nrany(i.e..P of them) small time "slices"r : t / p. onc then expresses the evolution operator as a productof P short-time propagators: itH\ rrHl \ -n (-r irHt e x /p ( - , , : . * o /l - - ) . - o ( -I ; , i) t. H / ; )

L ' * n \ -t / l



If one can developan efficient rneansof propagatingfor a short time r. one can then do so over and over again P times to achievethe desiredfull-time propagation. It can be shown that the exponential operatorinvoll'ing 11 can betterbe appro.ximated in terms of the f and I/ exponential operators as follows: / \exp rrH\ l

ft /-.*pt,-.

.tf -V \ p ( -/ - t-'F - ln .*



a /.-o(_;/


So. if one can be satisfied with propagating for very short tirne ir.rtervals (so that the rl term can be neglected), one can indeeduse

-*p(-+)-'(-T) *'(-#)


as an approximation for the propagator U(r, 0). To progressfurther, one then expresses exp(-irT//1) acring on the initial function v(q) in terms of the eigenfunctions of the kinetic energy operator r. Note that these eigenfunctions do not dependon the nature of the potential z, so this stepis valid for any and all potentials. The ei_eenfunctions of r :

/ tntd'/ctq'




, ! , , ( q ) : ( * )* '" r(T)

( 1.e6)

M o t i o no f a p a r t i c l e in one dimension


andthey obeythe following orthogonality f J relations andcompleteness J Writing V(q) as rL,.t,t trlr,",tt1 \lp = |rq - q t. 3rp - pl V i , t a t t l r , , ( q t: dq

(r . 9 7 )

(r . e 8 )

v ( q ) : I A u- ( ] ' ) v ( q ' ) d q , .
expression andusingthe above for d(q - q') gives

(1 . e 9 )

rr(q) :

| |

(q'ytq' ttp. v,,u,,,t';,,q' )rtt


theexplicitexpressions Tlreninsertin-e for tlr ,(c1)andr!;(q' ) in termsof ,,ft 1: ,,1c1 r'z pr7 exp(i 0 l2ir 1t /fi) -erves . Q t ' 7 t :f f l JI \; I tr:

i7r4171r: / i p ut ' * o1 (; l (;,) ..-o ( - # ) Q r 't 1 't'1'tprrr0rt

Now.allor.ving exp(-i r T lIt)to act on this form for W(r7) produces rr / ; ' , ' r t i \ /I / irT\ \'' ..P ( )wtq,: n JJ . ' p ( ' # l l r ; t ,l ^ . *' o L [ ? , u : , , f : ) ' ' ' * , r , r o r , r , ( rr 0 2 ) h

) \ h t The integralover p abovecan be carriedout analyticallyanclgives

. * P/ (


n ) q , , t , : ( : r , r , ) 7 . * oL

1 m r : /

l f i n r q _ 4 ' t :\ ttt,t'),t"t



So, the final expressiontbr the short-time propagatedwave function is v :. *L o[-irli'l "{' ,,r ."r-) " u


-1 (t7:1 tf , nt \'t f -.^fint1t (.,,r/



{1.10+) lVtt1'td,l.

whichis theworkingequation oneuses to compute V (q , t )knowingV (4). Notice thatall oneneeds to kno."r, to applythis formulais the potentia 1 v (q) ateach pornt ln space. one doesnot needto know anyof the eigenfunctions of the Hamiltonian to apply this method.Howe'u'er. one doeshaveto use this formula over and over agarnto propagate the initial wavefunction throughmany small time stepsr to achieve fr"rll propagation for the desired time intervalt : pt. Because thistypeoftime propagation technique is a very activeareaofresearch in thetheorvcommunity. it is likely to continue to berefinedandimproved. Further discussion of it is beyondthe scopeof this book, so I will not go further in this direction.

T h eb a s i c s o f q u a n t u mm e c h a n i c s

1.4 Freeparticlemotions in more dimensions

T h e n u m b e ro f d i m e n s i o n s d e p e n d so n t h e n u m b e ro f p a r t i c r e s and the number of spatial {and other) dimensions needed to characterize the positionand motion of each particle.

1.4.1 T h e S c h r o d i n g ee rq u a t i o n
consideran electronof massri and chargee mo'rng on a tlvo-dimensionar surface thatdefines thex, -r.plane (e.g., perhaps an electron is constrained to the surfaceof a solid by a potentiarthat binds it tightly ro a narro\\,regio' in the ---directio.). and assume that the electron experiences a constant and not trrnevarvrngpotentialI1t at all pointsin this plane.The pertinent tinre-independent Schrodinge cr quation is -t t a t\.. /a t + 'drt \a"t' )t(r't')* L i t l t ( x " r ' ) :E f ( ' r " r ' ) (1 10-5)

The task at hand is to solve the aboveeigen'alueequation to deternrine the "allorved" energystates for this electron. Because thereareno termsin this equa_ tion thatcouplemotionin the; and l directions (e.g.. no ternlsof the form,t,-r.b or Sldx 0/Ev or x 0/8v),separation of'u'ariabres canbe used rowrite y'rasaproduct U(r. -r'): l(.r)BLr,). Substitution of thisforrnintotheSchriidinger equarion, followed by collecting together all r-dependent andall _r'-dependent terms,_qrves

rf 1a]A rt ta2a
2*7ar;2-E *:E-rtt'


Since the first term contains no r,-dependence and the second contains no x-dependence. and because the right sideofthe equation is independent ofboth x and -r,,both terms on the left must actuallybe constant(thesetwo consranrs are denoted E" and Er', respectiveiy). This observationailows two seDarare Schrcidinger equations to be written:
- - / - ' - - F ztn dx.


. alA



^-, fB = - il b r)'' 2m ai


The total energyE can then be expressed in termsofthese separate energies E, and E, as E, + E:, : E - 20. Solutionsto the x- and .quations ,t,-Schrcidinge. areeasilyseento be:

A(x):*o[,,. (+)"'] B(,r'):.*p[,r, (ry)"]

. ano

| / 2 n E .t ' - | expl-ilt -.1 | \ t r / L l



a n d . ^ o [ -( ,, +)"1
L \ r

( rr o )

F r e ep a r t i c l e m o t i o n si n m o r e d i m e n s i o n s


solutions are obtained for eachequation because the,r- and Trio independent equations are Schrodinger both second order differential (i.e.. equations .r.-space differential equation order has two independent solutions). a second

conditions 1 , 4 . 2B o u n d a r y
T h e b o u n d a r y c o n d i t i o n s ,n o t t h e S c h r o d i n g e re q u a t i o n ,d e t e r m i n e s ill be discrete w h e t h e rt h e e i g e n v a l u e w or continuous. is entirelyunconstrained If theelectron within the-r. _r' plane, theenergies E, any values:this meansthat the experimenter and 8.,.can assume can "inject" onto the,r.r'plane with any total energyE and any components rhe electron alongthe two axesas long as E^ + E;. : E .In sucha situation. 8., and ^t.,. one ofthe energies alongbothcoordinates speaks asbeing"in thecontinuuln" or'.not quantized". In contrast. if theelectron is constrained to remain within a fixedarea in the.r.,r, (e.g., plane a rectan-eular or circr.rlar region), thenthe situation is qualitatively dif'i'erent. constrainin-e the electronto any suchspecified areagivesriseto boundary conditions thatimpose additional requirements on the above A anJB fLrnctrons. These constraints can arise, for example, if the potentiall,ii(.r. becornes verv _r,) Iarge tbr,r. .i values oulside theregion, in r,vhich case rheprobability of fincjine the electron outside theregion is very small.Sucha case mightrepresent. for example. a situation in rvhich thentolecular structurc ofthc solid surface changes outsidc the enclosed regionin a \\'aythatis hi-uhly repulsive (e.g.. to rheelectron asin thecase of molecular corrals on metalstrrfaces). This casecouldthenrepresent a simple "corrals" modelof so-called in rvhichtheparticleis constrained to a finiteresion of space. Forexarnple. if rnotion is constrained to takeplacelvithina rectaneular regron defined b y 0 . - r < l , : 0 < , r . < 1 . , . t h e nt h e c o n t i n u i t y property t h a ta l l w a v e tunctionsrnustobev (because of their interpretation as probabilitydensities. whichmustbe continuous) causes I ("r) to vanish at 0 andat r , . Thatis. because .'1 mustr.'anish fbr.r < 0 andmustl'anish for.v > z.r,andbecause A is continuous. itmustvanishat,r:0andat.r:2.,.Liker.r,ise.B(rr)mustvanishat0andatZ... To inrplemc'nt these constraints for I (.r: ). onemustlinearlycombinetheabovetwo solutionsexp[i,r(2 Er,rl l i 2 l t i z l a n d e x p [ - r . r ( 2 n E , y / t 2 l r i z l t o a c h i e v e i i f u n c t i o n thatvanishes at,r : 0:

"] r(r1: e1p(rf)'"] -.*o l', [-,,{i+)

(r.ll )

one is allowedto linearlycombinesolutions of the Schrodinger equation that havethe sameenergy(i.e.,are de,eenerate) because Schrcidinger equations are


T h e b a s i c so f q u a n t u mm e c h a n i c s

li,ear differentiar equations' An analogous process must be appried to g(,r,)to achieve a functionthatvanishes at.r,: 0.

Furtherrequirin-e A(.r) andB(rr) to,,,anish. respecti'elrr _ 2,. at.r : Z.\ and_r, s r i e se q u a t i o nts h a rc a nb e o b e y e d o n l y i f , f , a n d E , a s s u n rp ea r t i c u l av ra l u e s : T . r n 1 , , , / 2 n Et t : f

B(r -op .. 12,,r, (t+!\"'l -.*" -;//1 1 :.1 'L f,.', \ t i I l - q \ fr ) L( J





,iarE,1i:l ) l - e r n J - i(r; ' ) l = ' ,l

r ir . , r

f , 2ntE rl 1116 i, [ l - ' r /' ] e r jP r, ir . ( f ' ^ n \ L " ) I , J ;L - ) ll : , These equations areequivalent (i.e..usingexp(i.r): . [ , l r1\2 l :)l s, '- n (n - t-E F; lcos-r, * i sin_i,)to


Knou,ing t h a rs i ng v a n i s h e a ste- nn,forz : l. 2. 3. . . . lalthough t h es i n ( z r ) function'u'anishes for n :0, this function'anishes for all -t or.r,,andis therefore unacceptabre because it represents zeroprobabiritydensityat alr points in space). one concludes that the energies E, a'd.E, canassume o'ly'alues that obey \ / r / . 1 2 n E ,\ r ' 2 r'I :n,r, ' .l - /l \ f

l = . i n l z( J L ' ri / J:u

r l a i E ,l r : l



t 1,,, tr

, l/2


(t.ll6) (1.t17) (l.rl8)

uith n\ and

t ff n d u d k

, - nlr2rt
zilr Li t,


t l , = 1 . 2 . 3 , . . . ( l . l1 9 )

It is important to stressthat it is the imposition of boundary conditions, expressingthe fact that the electron is spatia'y constrained that gives ,se to quantized energies. In the absence of spatialconfinement" or wjth confinement only at;r : 0 or Z, or only at y _ 0 or 2.,, quantizedenergieswould rot be realized. In this exampre,confinementof the erectronto a finite interval along both the 'r and 'r" coordinates yields energies that are quantizedalong both axes. If the electronis confined"t:lg:l".oJrdinur. 1.g., u.t*".n 0 < x < 2..) bur not along the other (i.e., Blu) is eitherrestrictea ioi,anist aty - 0 or at .1, : L,. or at neirherpoinl). thenthetoralenergy E liesin th, mo.i than enouj energy in one of its bonds to

iinear triatomic morecurehus

isquantizld u,i r, i, ""t.Anarogs orsuch ;:Tl'.::T;:li.*r;:,TiffT

F r e ep a r t i c l e m o t i o n si n m o r e d i m e n s i o n s


ruprureit but not much ener,{yin the other bond; the first bond,sener-ev lies in the second bond'senergyis quantized. the"rt moreinteresting Perhaps is thecase in whichthebondwith the higherdissoci_ is ercited to a levelthatis not enough ationenergv to breakit but that is in excess energyofthe weakerbond.In this case. ofthe dissociation onehastw.odegenerate (i) the stron-s bond havinghi-eh states: internalener-qy and the weak bondhaving (/r). and (ii) the stron_e low energy bondhavinglittle energy andthe weakbond ha'ing more thanenoughenergyto ruptureit (tL). Althou_eh an experimenr may the moleculein a statethat contains prepare only the former component (1.e., rlt : Crltr -f C1r2.with cr - l. c: : 0), coupringbetrveen the two degenerate functions(inducedby terms in the HamiltonianH that havebeen ignoredin and ry'2) definingry'1 usuallycauses the true wave function W : exp(_il Hih){., to acquirea component of the second functionastime evolves. In sucha case, one of internal speaks vibrational energy relaxation (IVR) givingriseto unimolecular decomposition of the nrolecule.

1 . 4 . 3E n e r g i e s andwavefunctions f o r b o u n ds t a t e s
For discreteenergy revers, the energiesare specifiedfunctionsthat depend on quantum numbers, one for each degree of freedom that is quantized. Returning to thesituarion i'which motionis constrained alongbothares.the resultant total energies and wavefunctions (obtained by inserting the quantum ener_cy levelsinto the expressions for '1(,r)g( r.)) are as follor,",s:
,l:iT- tT


2nLi n:n-lr
tnt Ll.

(r . 1 20) ( r .r 2 l ) 1.t22)
T , : , ,

t r _ ' - :

1 | \ : / I \

y'( r ,: ( + ) ( # ) ' L * o ( " F - .)* o ( # ) ]

.[.-o( +)-.-,(-i:)]
w i t h n , a n di l , = ! . 2 , 3 , . . . (L.l:l)

The two (1/2Dt/2 factorsare incruded to guarantee that ry'is normalized:

t tx v: I wo.1,)l2d

( L 12,{)

Normalization allowsltL(x , y)r2to be properly identified asa probabiliry density for findingthe electron at a point-lr. r,.


T h e b a s i c so f q u a n t u m m e c h a n i c s

rffi) wl

Plots of the

( a )( 1 , 1 )(,b )( 2 , 1 )(,c ) { 1 , 2a ) n d \ d l Q , 2 lw a v e f un c t i o ns.

Shou'nin Fig. l.l3 are plots of four suchtwo-dimensional u,avefunctions f o r r r . a n dn , v a l u e s o f ( 1 , 1 ) ,( 2 , 1 ) ,( 1 . 2 )a n d ( 2 . 2 ) .r e s p e c t i ' c l .N vo . r e t h a tt h e functions vanishon the boundaries of the box, and noticehou,tlre nurnberof (i.e..zeroes nodes encountered as the r.r,ave functionoscillates fi-ompositiveto ne-qati\:e) is relatedto the r- and n.,.quantun nurnbersand to the energy.This patternof more nodessignifying higher ener_rly is one that u,e encounteragain and againin quantummechanics and is something the student shouldbe able to useto "guess"the relativeenergies of war.efur.rctions when their plots are at hand.Finally,you shouldalso in the one-dimensional box case. an)'attempt p(-r. corresponding to classically interpret theprobabilities to the -r,) above quanturn \4'ave functions will resultin failure.As in the one-dinrensionai case. theclassical P(.:r'. alongslices 1,)wouldbe constant of fixed.randvaryinu _i, orslicesoffired,r'andvarying-r r.r,ithintheboxbecausethespeedisconstantther Hou'ever, the quar.rtum P(x, t,) plots,at leastfor small quantumnumbers, arenot constant. For large p(r, r, andn ,.values, thequantum via the l,) plotswill again, quanturn-classical correspondence principle.approach the (constant) classical P(.r.,i,)form.

F r e ep a r t i c l e m o t i o n si n m o r e d i m e n s i o n s


a c t i o nc a n a l s o b e u s e dt o d e r i v e 1 . 4 . 4Q u a n t i z e d e n e r g yl e v e l s
that canbe usedto find energylevelsand is especially Thereis anotherapproach to use for systemswhose Schrodinger straightforward equations are separable. classical Theso-called action(denoted s) of a particre movingwith momentum p alonga pathleadingfrom initial coordinate q1at initial time ri to a final coordinate t i m er ; i s d e f i n e d by




Here.the momentufir vectorp contains the momentaalong all coordinates of the system.and the coordinatevector q likewisecontainsthe coordinates along all suchdegrees of freedom. For example, in thetwo-dimensional particle-in-a-box problem considered above, q : (" hastwo components as doesp : (p,.p,,), and the action integralis

In computin-u suchactions, it is essential to keep in mindthesignof themomentum as the particlemovesfrom its initial to its final positions. An example will help clarify'thesematters. Forsystems suchastheabove particle-in-a-box example for whichtheHamiltonianis separable, the actionintegral decomposes into a sum ofsuch integrals. one fbr eachdegreeof freedom.In this trvo-dimensional example,the additivity of H.

H : t i ,- H ,: + ti ;;t: - r


- + + v t y t 1v l v t 2n fi a2



I'{.t)- :-:-;

* l'( r').


means that p. and p.r.canbe independently solvedfor in termsof the potentials v(r) and I,'(,u) as well as the energies 6. and 6,, associated with eachseparate degree of freedom:

p, : +r/2i(.1rlo)), , / =t t-t l b - , - Y l . v l l ;

(r . r 2 8 )

the signs on p, and pr, must be chosento properly reflectthe motion that the particleis actuallyundergoing. Substituting theseexpressions into the action rntegral yields

f fi:rf



t f2n1E,- v(t))rr *

t vtrt))t/.v. (r.l-ll) Jr,,,, Jrm@,-


T h eb a s i c s o f q u a n t u mm e c h a n i c s

The relationship between theseclassical actionintegrals and the existence ol quantized energylevelshasbeenshownto involveequating the classical action for rnotionon a closed pathto an integral multipleof planck's corlstant: s . r n .= "d fqt=c' p : q: r i l r ( , : l . ] . 3 . : 1. . . ) . (1.132)

Appliedto eachof the independent coordinates of the trvo-dirnensional particlein-a-box problem, this expression reads
n . , l t= | J.-o

- !f/x(l' dt + | ,2tn(E, - I'(,r)) - l, = r.



(l ljj)


f,=t Jr:0

) l)r + t t 2 m ( E,1 " ( . r .t |


*r,1i1E _ t1ry1 ,lr.



Notice that the signs of the niomentaare positivein each of the first inreg r a l sa p p e a r i n a ( b e c a u st e gb o v e heparticle is mo'ing ()to.r-:1,. . n d t h u sh a sp o s i r i r e a n d a n a l o s o u s lfy o r . t - l t t o t i o na n r o n t c n t u l lr rn d n e l a r i r t i n e a c ho f t h e s e c o n d ( b e c a u ste inregrals h e r n o t i o ni s f r o m . r : l , t o - i - : 0 (andanalogously for.r'-motion) and thusthe particlehasnegative nromentum). W i t h i nt h e r e g i o n bounded b y 0 . - r -< l . : 0 < , r . < 2 , . t h c p o t e n t l av lanishes" so i/(x) : l'lr') : 0. Using this fact. and re'ersingthe upperanti lou,er linrits. andthusthe si-sn. in the second integrals above. one obtains
n,h:2 [ ' = t ' , ' 7 , , , qd r : 2 r 5 u , P 1 , . '=' n, h : 2 [ 1Zn t, tlt. : 2{r,, tr, L, (1.3 16) (l.li5)

Solving for E, and 8,. one finds (n,h12

6ri l-; (n'h\2


s nL l

Theseare the sarnequantizedenergylevelsthat arosewhen the u,avefunctron boundary conditions werematched atx : 0. r : 2., and,l : 0..1, : 1,,. In this case!one saysthat the Bohr*sommerfeldquantization condition.

nh :, lo't=o""


hasbeenusedto obtainthe result. Theuseof actionquantization asillustrated above hasbecome a very important tool. It has allowed scientiststo make great progresstoward bridging the gap between classical andquantumdescriptions of molecular dynamics. In particular,

F r e ep a r t i c l e m o t i o n si n m o r e d i m e n s i o n s


quantal concepts suchastrajectories andthenappending action by usingclassical people have been able to develop so-called models of semi-classical conditions. In suchmodels, dynarnics. oneis ableto retaina greatdealof classical molecular whiie building in quantumeffects such as energy quantization. understanding energies. and interf'erences. zero-point

a c t i o nd o e s n o t a l w a y sw o r k 1 . 4 . 5O u a n t i z e d
the approachof quantizingthe action does not alwaysyield the Unfortunately. for the quantized For example.when appliedto erpression energies. correct problemthat we will study in quantumform harmonicoscillator the so-called which serves as the simplest reasonable modelfbr vibrationof a diatomic later. AB. one expresses the totalenergy as molecule



A force hB e d i a t o m . firs t h e w h e r e 4: m ^ n t B l 0 n A f rrs) isthereducedmassoft describing thebondbetween A andB. r is thebond-length displacement. constant alongthebondlen-eth. The quantized actionrequirement andp is themomentum thenreads

: I pd : ,h , I l ' , ( ' -1 , ' ) ] ' ' , ,


y = - ( 2 8 l k ) l ' l a n dC E l k l ' 1 . t h el e f ta n d T h i si n t e - u r a i sl c a r r i e d o u tb e t w e e n path. to form a closed rightturningpoints of theoscillatory motion. andbackagain itto nh givesthe followin_q expression Carryingout this integraland equating for thc energyE:

6-:,,. l-l ::r

, , . 1 2 I I I K \



rvhere integer valuesranging from the qLlantum nunrber ri is allorved to assume n : 0. l. 2. to infinitv. rviththisresultis thatit is wrong! As experiThe problem mental dataclearlyshor'",. thelowest energy levels for thevibrations of a rnolecule do not haveE :0: thevhavea "zero-point" that is approrimately equal energy Lo I l2( h l21 11.1; the actionquantization conditionyieldsenI p\ti: . So.although ergies whosespacings in agreement rvith laboratory datatbl lorvarereasonablv (e.g..suchstates energy haveapproxirnately constant spacings), it fails to states predictthe zero-point a As we will seelirter, energy content of suchvibrations. properquantum yields the harmonic enc'rgies rrechanical treatment of oscillator of the ibrm " (1.143) E : (,,.:) (*)(:)
which differs from the oction-bascdresult by the proper zero-point energy.

The basics o f q u a n t u mm e c h a n i c s

Evenu'ith suchdifficulties knou'n. nruchprogress hasbeenmadein extending themostelementary action-based methods to moreandmoresvstems by introduc_ ing. for exanrple. rulesthat alloll the quantum numbern to assume half-integer a s ' " v e la l si n t e - q e r v a l u e sl . C e a r l 1i,1 . ' nu ' e r e allowed t o e q u a ll / 2 . 3 / 2 . 5 1 2 . . . . , the earlier actionintegral wouldhaveproduced the correctresult. However. hou, doesone know when to allorvr?to assume only integeror only harf-integer or both integerand half-integer values? The ansr.vers to this question are beyondthe scope ofthis text and constitute an activeareaofresearch. For no$,. it is enough for the studentto be awarethat one can often find energylevelsby,using action integrals. but onerrrust be careful in doingso because solnetlmes theanswers are wrong. Beforeleavingthis section. it is worth noting that the appearance of half-lb rnteger quantum numbers doesnot onlv occurin theharmonic oscillator case. illustrate. let us consider the r_- angularmomentum operator discussed earlier. As we showed this operator. when con.rputed as the ---component of r x p, can bewritten i n p o l a r( r . 0 . 6 ) c o o r d i n a t e as s
L_ : -ihd /d0. (l.l4l)

The eigenfunctions ofthis operator ha'e the forrr exp(ia@). andthe eigenvalues arenfi. Because geometries with azimuthal angles equal1o@or equalto Q * 2r areexactl)'the same geometries, thefu'ction exp(i a(t)should be exactly thesame 't hr 1).This can onrybe the case as exp(ia(Q if a is an integer. concludes thatonlyintegral multiples offi canbe'.allowed" values ofthe:-cornponent of angular momenturn. Experimentalry,, onemeasures the:-component of an anmomentum bi, placingthe system -eular possessing the a'gular momentum in a magnetic field of strengthB and obser'ing how many---corxponent energystates arise. Forexample, a boronatomwith its2p orbitalhasoneunit of orbitalangular one finds three separate ;-co,lponent 'alues r.l,hich are usually denoted nt : -7, m :0, andnt = L Anotherexample is offeredby the scan_ dium atom rvith one unpairedelectronin a d orbital: this atom,sstatessplit into five (rr = -2, -1. 0. 1, 2) z--component states. In eachcase. one finds ZL + l valuesof the r/r quantumnumber,and,because r is a' integer.2L + l is an odd integer.Both of theseobservations are consistent with the expectation that onlv integervaluescan occur for Z, eigenvalues. hasbeenobserved that somespecies do not possess 3 or 5 or 7 or 9:-component states but an evennumberofsuch states. In particular. whenelectrons,protons,or neutrons aresubjected to the kind of magneticfield experiment mentionedabo'e, theseparticlesare observedto have only two z-componenr eigenvalues. Because, as we discuss later in this text. all an-qular momentahave .?-component eigenvalues that are separated from one another by unit muiti_ ples of fi. one is forced to concludethat thesethreefundamental building-block particleshave:-componenteigenvalues -r of u2ri and. The appearance of /2h.

F r e ep a r t i c l e m o t i o n si n m o r e d i m e n s i o n s


momenta angular is not consistent with the observation madeearlier half-integer to exactlythe samephysicalpoint in coordinate that @and Q + 2;r correspond in turn,implies thatonly full-integer u'hich, angular momenta arepossible. space, (i.e., of the paradox above resolution horv half-integer can angularmoThe involved realizingthat someangularmomenta correspond not to mentaexist?) the r x p angularmomentaof a physicalmassrotating.but. insteadareintrinsic of certainparticles. That is, the intrinsicangularmomenta of elecproperties neutrons protons, and not can be viewed as from arising rotation of some trons, theseparticles.Insteadsuch intrinsic angularmomentaare massthat comprises "built in" characteristics of theseparticles.For example.the trvo fundamental momentum states of an electron, usuallydenoted o and I l2l1 and-112h angular p. respectively. are two internal states ofthe electronthat are degenerate in the of a magneticfield but which represent fwo distinct statesof the elecabsence a proton has I l2h and -l l2li states, tron. Analogousl,v, as do neutrons. All such angularmomentumstatescan not be accounted half-integer for using classical but are knorvnto arisein quantummechanics. mechanics