C AM B R I D !

E U N I V E R S I T Y P RE S S
C

F C L AY , M AN A ! E R
.

FE T T E R

L O N DO N

LO ND O N

K
1 36

N EW Y O R K

M B AY
CA L C U TTA
M A D RA S
TO R O N TO

LA

NE

L E W I S A N D CC

ow e r

S tr e e t ,

TH E

E C 4
.

L TD

.,

MACM I LLAN CO

BO

M AC M I LL AN

L TD

M AC M I LL AN C O O F
CANA D A L TD
M ARU Z E N K AB U S H I K I K A I S H A
TH E

TO K Y O

AN D C O

AL L

R I ! H TS R ES E R V E D

T he T h eo ry

of

Sp e c t ra

a nd

A t o m ic C o nst i t u t io n
TH REE ESSA Y S
BY

N I ELS
Profe s sor

of

R
H
O
Q

Th e or e t i c al Phy sics i f the U n iver s i ty of C ope n h ag e n

C A M B RI D ! E
AT TH E

V
I
I
T
N
E
R
S
Y
P
R
E
SS
U
1922

R I N TE D I N ! RE AT B R I TAI N
AT TH E CAMB R I D ! E U NI VE R S I TY P R E S S
P

P REFA C E

HE

three essays which here appear in E nglish all deal with

the application of the quantum theory to pro b lems of atomic
structure and refer to the different stages in the development of
this theory

The rst essay O n the spectrum of

hydrogen is a translation of
a D anish address given before the P hysical S ociety of C openhage n
and printed in Fys i s /c Ti ds s kmft
on the 20 t h of D ecember 19 13
X I I p 9 7 19 14
A lthough this address was delivered at a tim e
when the formal development of the quantum theory was only a t
its beginning the reader will nd the general trend of thought
very similar to tha t expressed in the later addresses which
form the other two essays As emphasized at several points the

theory does not attempt an explanation in the usual sense of

this word but only the establishment of a connec t ion between facts
which in the present state of science are unexplained that is to
s a y the usual physical conceptions d o not o ffer su fci e n t basis for
a detailed description

The second essay O n the series spectra of the elements is a

translation of a ! erman address given before the P hysical S ociety
of Be r lin on the 27 t h of A pril 19 20 and printed in Z ei ts chr i t r
f f
P hys i k V I p 423 19 20 This address falls into t wo main parts
The considerations in the rst part are closely related to the con
tents of the rst essay ; especially no us e is made of the n e w
formal conceptions established through the later develop ment of
the quantum theory The second part contains a survey of the
results reached by this development A n attempt is made to
elucidate the problems by means of ageneral pri nciple which post u
lates a formal correspondence between the fundamentally di fferent
conceptions of the classical electrodynamics and those of the
quantum theory The rst germ of this co rrespondence principle
may be found in the rst essay in the deduction of the ex
pression for the constant of the hydrogen spectrum in terms of
P lanck s constant and of the quantities which in Rutherford s
,

P R EF A C E

atomic model are necessary for the description of the hydrogen

atom

The third essay The structure o f the atom and the physical
and c h emical properties of the elements is based on a D anish
address given before a j oint meeting of the P hysical and C hemical
S ocieties of C openhagen on the 18 th of O ctober 19 21 and printed
in Fys zs k Ti ds s kmf t X I X p 15 3 19 21 While the rst two essays
form verbal translations of the respectiv e addresses this essay
di ffers from the D anish original in certain minor points Besides
the addition of a few new gures with explanatory text certain
passages dealing with problems discussed in the second essay are
left ou t and some remarks about recent contributions to the
s u bj ect are inserted Where such in sertions have b een introduced
will clearly appear from the text This essay is divided into
four parts The rst two parts contain a survey of previous results
concerning atomic problems and a short account of the theoretical
ideas of the q u antum theory In the following parts it is shown
h ow these ideas lead to a view of atomic constitution which seems
t o o ffer an explanation of the observed physical and chemical
properties of t h e elements and especially to bring the character
i s ti c features of the periodic table into close connection with th e
interpret a tion of the optical and high frequency spectra of the
e lements
For the convenience of the reader all three essays are su b divided
into smaller paragraphs each with a headline C onforming to the
character of the essays there i s however no question of anything
like a full account or even a proportionate treatment of the subj ect
stated in these headlines the principal obj ect being t o emphasize
certain general views in a freer form than is usual in scientic
treatises or text books For the same reason no detailed references
to the literature are given although an attempt i s made to mention
the main contributions to the development of the subj ect As
regards further information the reader in the case of the second

essay is referred to a larger treatise O n the quantum theory of

line spectra two parts of which have appeared in the Transactions of

the C openhagen A cademy (D Kgl D a ns ke Vi dens k S els k S kr if ter
8 B aekk e 1V 1 I and II 19 18 ) where full references to the literature
m a y be found The proposed continuation of this treat i se m e ntioned
.

P R EF A C E

vii

at several places in th e second essay has for vario u s reasons b e en

delayed b u t in the near future the work will be completed by the
publication of a third part I t is my intention to deal more fully
with the problems discussed in the third essay by a larger syste
matic account of the application of the q u antum theory t o atomic
problems which is under preparation
A s mentioned both in the b eginning an d at the end of th e
third essay the considerations which it contai n s are clearly still
incomplete in character This holds not only as regards the
e laboration of details b u t also as regards th e development of the
theoretical ideas I t may be u seful once more to emphasize

that althou gh the word e xplanation has b e en u sed more

liberally than for instance in the rst essay we are not concerned
with a description o f the p henomena based on a well d e ne d
physical picture It may rather be said that hitherto e very
progress in the pro b lem of atomic structure has tended t o emphasize

the well known mysteries of the quantum theory more and more
I hop e the exposition in these essays is sufcien tly clear nev e r
t h e l es s t o give the reader an impress i on of the peculiar charm
w hich the study of atomic physics possesses j ust on this account
I wish to e xpress my b est thanks to D r A D U dden University
of P ennsy lvania who has undertaken the translation of the
original addresses into English and t o Mr C D E llis Trinity
C ollege C ambridge who has looked through the manuscript and
suggested many valuable i mprovements in the e xposition of the
subj ect
N B O HR
,

C O PEN H A ! EN ,

Ma y

19 22

C O N TEN TS
ES S AY

O N T HE S PECT RU M OF HY D RO ! E N

A E

P !

E mp i r i c a l S p e ctra l L a ws
L a ws of T e m pe r a tu r e Ra di a t i on
Th e N u clea r Th eory of th e Atom
Qua ntu m T h eory of Sp ectra
Hy drogen S p ec tr u m
Th e P i ck er i ng L i nes
O t h e r S p e ct r a

ESS A Y

10
12
15
18

II

ON T HE S E R I E S S PE CT RA OF TH E E LE ME N TS

II

IN TRO D U CTI O N
! ENE RAL PR I NC I PL E S

2O
OF TH E

QUA NTUM

T H E O RY

OF

S PE C TRA

Hy d r ogen S p ec t r u m
Th e C or r e s p onde nc e Pr inc i p l e
! ener a l S p ec t r a l L a w s
A b s or p t i on a n d E xc i t a t i on of Ra d i a t i on
III

D E VE L O PM EN T OF TH E

UA

N T UM T H E O RY

24

29

OF

S P E C TRA

E ffect of E x ter na l F orc es on t he Hy d r ogen S p ect ru m

Th e S t a r k E ffec t
Th e Z ee ma n E ffec t
Ce ntr a l Per tu r ba t i ons
Re l a t ivi ty E ffec t on Hy d rogen L i nes
T h eory of S e r i es S p ectr a
Cor r e s p onde nc e Pr i nc i p le a nd C ons erva t i on of Angula r Mo
me ntu m
Th e S p ec tr a of Heli u m a nd L i th iu m
C omp le x S tru c ture of S eri e s L i nes
IV

CO NC L U S IO N

23

36
37

39
42
44
46

48
50

54
58

59

C O N T E N TS

ESS A Y

III

TH E ST R U CT U R E O F T HE A T O M A N D T HE P H Y S I C AL
A N D C H EM I C AL P RO PERT I ES O F THE ELEM EN TS
A E

P !

PRELI MI NAR Y

The N u cl ea r Atom
Th e P os tula t es of th e Q
u a nt um Th eory
Hy dr ogen At om
Hy droge n S p ec tru m a nd X
r a y S p ec tra
Th e F i ne S tru ctur e of th e Hy drogen L i nes
P er i od i c T a ble
R ecent At omi c Models
II

S E R IE S S PE C TRA

Ar c

AN D TH E

CAPT UR E

OF

ELECTR O N S

BY

AT OMS

S p a rk S p e ctra
Di a gr a m

a nd

S eri e s
C orr es p onde nc e Pri ncip l e

III

FO R MAT IO N

OF

ATO M S

AN D TH E

PE R IO D I C TA B L E

H y d r ogenH eli u m
S e cond Peri od L i t h iu mN e on
T h ir d P er i od S od iumAr g on
F our th Per i od Pot a s s i u m Kr yp t on
F ifth Per i od Ru b id i u mXenon
S i xth Pe r i od C ae s i u m N i t on
S e venth P eri od
S u r vey of th e Per i od i c Ta bl e

F ir s t

P e r i od

100

10 8

10 9

IV

REO R ! A N I Z AT IO N
Ab s orp t i on

a nd

OF

AT OMS

AN D

E mi s s i on of X
ra y s

RAY
a nd

ra

S
y p e ct r a

a nd

C la s s i ca ti on of X
CO NC L U S IO N

113

S PE C TRA

116

C orre s p on den ce Pri n

117

c i pl e

11 1

A tomi c S tr u c ture
ray

S p e c tr a

119

121

125

ES S AY 1
ON

TH E

S PE CTR U M

OF

HY D R O ! EN

e c t r a l l a w s Hydrogen possesses not only the

smallest atomic weight of all the eleme n ts b u t it also occupies a
peculiar position both with regard to its physical and its chemical
properties O ne of the points where this becomes partic u larly a p
parent is the hydrogen line spectrum
The spectrum of hydrogen observed in an ordinary ! eissler tube
consists of a series of lines the strongest of which lies a t the red
end of the spectru m while the others extend ou t into the u ltra
violet the distance between the various lines a s well as their i n
te n sities constantly decr e asing In the ultra violet th e s e ries con
verges t o a limit
Balmer as we k n ow discovered ( 18 85 ) that it was possi b le to
represent the w a ve lengths of these lines v e ry acc u rately by th e
s imple law
E mp i r i c a l

sp

R
n

1
( )

where R is a constant and n is a whole num b er The wav e lengths

o f the ve strongest hydrogen lines corresponding t o n
3 4 5 6
7 measured in air at ordinary press u re and temperat u re a nd the
.

values

of

th e se wa ve lengths multipli e d by

the following table :

A

1\

are give n i n
2

71

n2

6 5 63 0 4

9 115 3 3

4 8 6 14 9

9 115 2 9

4 3 40 6 6

9 115 3 9

4 10 18 5

9 115 22

3 970 2 5

10m

The table shows that the product is nearly constant whil e the devia
tions are n ot greater than might be ascribed to experim e nt a l errors
A s you already kno w B a lme r s discovery of the la w relating to
the hydrogen spectrum led to the discovery of laws applyi ng to
the spectra of other elements The most important work in this
A d dr es s d eliver e d be for e th e Ph y s i c a l S oci e ty i n C op e nh a ge n De c 20 19 13
,

ON T HE S PE C T RU M OF HYDR O GE N

connection was done by Rydberg ( 18 9 0 ) and Ritz

Rydberg
pointed out that the spectra of many ele ments contain series o f
lines whose wave lengths are given approximately by the formula
1

(n

oz

where A and a are constants having di fferent values for the various
series while R is a universal constant equal to the constant in the
spectrum of hydrogen If the wave lengths are measured in vacuo
Rydberg calculated the value of R t o be 10 9 6 7 5 In the Spectra of
ma ny e le m e n ts as opposed to the Simple spectrum of hydrogen there
are several series of lines whose wave lengths are to a close a p pr ox i ma
tion given by Ryd b erg s formula if different values are assigned to
the constants A and a Rydberg showed ho wever in his earlies t
work that certain relations existed betwee n the constants in the
various series of the spectrum of on e and the same eleme n t These
relations were later very successfully generalized by Ritz through

the establishment of the combination principle

A cc ording to
this principle the wave lengths of the various lines in the spectr u m
o f an element may be expressed by the formula
,

F,

In this formula 72 and n are whole numbers and F (n) F (n)

is
a series of functions Of n which may be written approximately
,

at

where R is Rydberg s universal constant and a is a constant which

is di fferent for the di fferent functions A particula r spectral line will
according to t h is principle correspond to each combination of n
and 71 as well as to the functions F F
The establishment of
this principle led therefore to the prediction of a great number of
lines which were n ot included in the spectral for mulae previously
considere d and i n a large number of cases the calculations were
found to be in close agreement wi th the experimental O bser vations
In the case of hydrogen Ritz assumed that formula ( 1) was a speci al
case of the general formula

1,

2,

2,

1
x

3
( )

O N T HE S PE C TRUM OF HYDROG E N

and therefore predicted among other things a series of lin es in the

infra red given by the formula
1

In 19 0 9 Paschen succeeded in observing the rs t two lines of this

series corresponding to 72 4 and n 5
The part played by hydrogen in the development of ou r
knowledge of the spectral laws is not solely due to its ordinary
simple spectrum but it can also be traced in other less direct
ways A t a time when Rydberg s laws were still in want of
further conrmation P ickering ( 18 9 7 ) found in the spec trum of a
star a series of lines whose wave lengths sh owed a very Simple r e
lation to the ordinary hydrogen spectrum Since to a very close
approximation they could be expressed by the formula
.

(
Ryd b erg considered these lines to represent a new series of lines
in the spectrum of hydrogen and predicted according t o his theory
the ex i stence O f still another series of hydrogen lines the wave
lengths of which would be given by
A

i gr

By examining earlier observations it was ac tually found that a line

had been observed in the spectrum of certain stars which c om el de d
closely with the rst line in this series ( corresponding to n :
from analogy with other spectra it was also to be expected th at this
would be the strongest line This was regarded as a great tri u mph
for Rydberg s theory and tended to remove all doubt that the new
spectrum was actually due to hydrogen Rydberg s vie w ha s there
fore been generally accepted by physicists u p to the present moment
Recently however the question ha s bee n reopened and F owler
1
12
9
has
succeeded
in
observing
the
P
ickering
lines
in
ordi
n
ary
)
(
laboratory experiments We shall return to this question again
later
The discover y of these beautiful and simple laws concerning the
line spectra of the elements has naturally resulted in many attempts
at a theoretical explanation S uch attempts are very alluring
.

ON T HE S PE C T RU M OF HYDROG E N

be ca use the Simplicity of the spectral laws and the exceptional accu
racy with which they apply appear to promise that the correct e x pla
nation will b e very simpl e and will give valuable information
a bout the properties of matter
I should like to consider some of
these theories somewhat more closely several of w hich are extremely
interesting and have been developed with the greatest keenness
a nd inge nuity but unfortunately space does n ot permit me to do
I shall have to limit myself to the statement that not
s o here
on e of the theories so far propos e d appears t o o ffer a satisfactory or
even a plau sible way of explaini n g the laws of the line spectra
C onsidering our decient knowledge of the laws which determine
the process es inside atoms it is scarcely possible to give an explana
tion of the kin d attempted in these theories The inadequacy of
our ordinary theoretical conceptions has become especially apparent
from the important results which have been Obtained in recent years
from the theoretical and experimental study of the laws of tem
Y
ou will therefore underst a nd that I shall not
e r a t u r e radiation
p
attempt to propose an explanation of the spectral laws ; on the
c ontrary I shall try to indicate a way in which it appears possibl e
t o b ring the spectral law s into close connection with other pro
e r t i e s of the elemen t s which appear to be equally inexplicab le on
p
the basis of the present state of the science In these considerations
I shall employ the results obtained from th e study of temperature
ra dia t io n as well as the view of atomic stru cture which has b een
reached by the study of the radio a ctiv e elem e nts
.

n I shall commence by men

t i on i ng the conclusions which hav e b een draw n from experimental
and theoretical work on tempera ture radiation
L et us consider an enclosure surro u nded by b odies which are in
temperat u re equilibrium I n this space there will be a certain
amount of energy contained in the rays e mitted by the surrounding
substances and crossing each other in every direction By making
the assumption that the temperature equilibrium will not be d i s
t u r b e d by the mutual radiation of the various bodies Kirchho ff
f
1
showed
that
the
amount
o
energy
per
u
n
it
volume
as
well
8
0
6
(
)
as the distribution of this energy among the various wave lengths
i s i n dependent o f the form and size of the space and O f the nature
L aw s

of

t em p er a tu r e

r a d i a ti o

ON T HE S P E C T RUM OF HYDROG E N

of

the surrounding bodies and depends only on the temperature

Kirchho ff s result has been conrmed by experiment and the
amount of energy and its distribution among the various wave
lengths and the manner in which it depends on the tempe
rature are n ow fairly well known from a great amoun t of e x p e r i
mental work ; Or as it is usually expressed we have a fairly

accurate experimental knowledge of the laws of temperat u re

radiation
Kirchho ff s considerations were only capable of predicting the
existence of a law of te m perature radiation and many physicists
have subsequently attempted to nd a more thorough explanation
Y ou will perceive that the electro
o f the expe r imental results
magnetic theory O f light together with the electron theory suggests
a method of solving this problem A ccording to the electron theory
By making
of matter a bo d y consists o f a system of electrons
certain denite assumptions concerning the forces acting on the
electrons it is possible to calculate their motion and consequently
the energy radiated from the body per second in the for m of
electromagnetic oscillations of v arious wave lengths In a simil a r
manner the absorption of rays of a given wave l e ngth by a substance
can be determined by calculating the e ffect of electromagnetic
oscillations upon the motion of the electro ns H a ving investigated
the emission and absorption of a body at all temperatures and for
rays of all wave lengths it i s possible as Ki rchhoff has shown to
determine immediately the laws of temperature radiation S ince
the result is to be ind e pendent of the nature of the body we are
j ustied in expecting an agreement with experiment eve n though
very special assumptions ar e made abo u t the forces acti ng upon
the electrons of the hypothetical substance This naturally
Simplies the problem considerably b ut it is neverthel e ss s u f
difcult
and
it
i
s remarkable that it has been possible
c i en tl
y
to make any advance at all in thi s direction AS is well known
this has been done by L orentz
H e calculated the
emissive as well as the absorptive power of a metal for long
wave lengths using the same assumptions about the motion s
o f the electrons in the metal that
D rude ( 19 0 0 ) employed in
his calculation of the ratio of the electrical and thermal condu e
S ubsequently by calculating the ratio of the emissive
t i v i t i es
.

O N THE S P E C TRUM OF HYDROG E N

the absorptive power L orentz really obtained an expression

for the law of temperature radiation which for long wave lengths
agrees remarkably well with e x perimental facts I n spite of this
beautiful and promising result it has nevertheless become apparent
that th e electromagnetic theory is incapable of e x plaining the law
F or it is possible to Show that if the
of temperature radiation
i nvestigation is not conned to oscillations of l ong wave lengths
as in Lor en tz s work but is also extended to oscillations corre
results
are
obtained
which
are
s on di ng to small wave lengths
p
contrary to experiment This is especially evident from Jeans
investigations ( 19 05 ) in wh i ch he employed a very interesting
statistical method rst proposed by L ord Rayleigh
We are therefore compelled to assume that the classical electro
dynamics does not agree w ith reality or expressed more carefully
that it can not be employed in calculating the absorption and
emission of radiation by atoms F ortunately the law of temperature
radiation has also successfully indicated the direction in which the
necessary changes in the electrodynamics are to be sought E ven
before the appearance of the papers by L orentz and Jeans P lanck
had
derived
theoretically
a
formula
for
the
black
body
radia
1
0
9
0
)
(
tion which was in good agreement with the results of experiment
P lanck did not limit himself exclusively to the classical electro
dynamics but introduced the further assumption that a system of
oscillating electrical particles ( elementary resonators ) will neither
radiate nor ab sorb energy continuously as required by the ordinary
electrodynamics but on the contrary will radiate and absorb dis
continuously The energy contained within the system a t any
moment is always equal to a whole multiple of the s o called
quantum of energy the magni tude of which is equal to b y where
h i s P lanck s constant and v is the frequency O f oscillation of the
system per second In formal respects P lanck s theory leaves m uch
to be desired ; in certain calculations the ordinary electrodynamics
is used while in others assumptions distinctly at variance with it
are introduced without any a t tempt being made to Show that it
is possible to give a consistent explanation of the procedure used
P lanck s theory would hardly have acquired general recogn ition
merely on the ground of its agreement with experiments on black
b ody radiation but as yo u know the theory has also contributed
to

ON

THE S PE C T RU M OF HYDR O GE N

quite remarkably to the elucidation of many di fferent physical

phenomena such as specic heats photoe l ectric effect X rays and
the absorption of heat rays by gases These explanations involve
more than the qualitative assu m ption of a discontinuous trans
formation of energy for with the aid of P lanck s constant it it
seems to be possible at least approximately to account for a great
number of phenome na about which nothing could be said previously
It i s therefore hardly too early to express the opinion that whatever

the nal explanation will be the discovery of energy quanta

must be consi d ered as one of the most important results arrived at
in physics and must be taken into consideration in investigations
of the properties of atoms and particularly in con n ection with any
explanation of the spectral laws in which such phenomena as
the emission and absorption of electromagnetic radiation are
concerned
-

n u c l e a r th e o ry o f th e a t om We shall now consider the

second part of the foundation on which we shall b uild namely the
conclusions arrived at from experiments with th e rays e m itted by
rad ioactive substances I have previously here in the P hysical
S ociety had the opportunity of speaking of the scattering of a ra ys
in passing through thin plates and to mention how Ru therford
1
o f the atom in
1
has
proposed
a
theory
for
the
structure
1
9
(
)
order to explain the remarkable and unexpected results of these
experiments I shall therefore only remind you that the charac
t e r i s ti c feature of Rutherford s theory is the assumption of the
existence of a positively charged nucleus inside the atom A number
of electrons are suppose d to revolve l n closed orbits around the
nucleus the number of these electrons being su fcient to neutralize
the positive charge of the nucleus The dimensions of the nucleus
are supposed to be very small in comparison with the dimensions
of the orbits of the electrons and almost the entire mass of the
atom is supposed to be concentra ted in the nucleus
A ccording to Rutherford s calcu lation the positive charge of the
nucleus corresponds to a number of electrons equal to about half
the atomic weight This number coin cides approximately with the
number of the particular element in the periodic system and i t is
therefore n atural to assume that the number o f electrons in the
Th e

ON

T HE S P E C TRUM OF HYDR O G E N

atom is exactly equal t o this n um b er This hypothesis which was

rst stated by v a n den Broek
opens the possibility of
obtaining a simple explanation of the periodic system This as
sum ption is strongly conrmed by experiments on the elements
of small atomic weight
In the rst place it is evident that a o
cording to Rutherford s theory the a particle is the same as the
nucle us of a helium atom S ince the a particle has a double positive
charge it follows immediately that a neutral helium atom contains
t w o electrons
F urther the concordant results obtained from cal
c u l a t i ons based on experiments as different as the di ffuse scatter
ing of X rays and the decrease in veloci ty of a rays in passing
through matter render the conclusion extremely likely that a
hydrogen atom contains only a Single electron This agrees most
beautifully with the fact that ! ! Thomson in his well known
experiments on rays of positive e lectricity has never observed a
hydrogen atom with more than a Single positive charge while all
other elements investigated may have several charges
L et us n ow assume that a hydrogen atom simply consists of a n
electron revolving around a nucleus of equal and opposite charge
and of a mass which is very large in co mparison with that of th e
electron It is evident that this assumption may explain the peculia r
position already referred to which hydrogen occupies among the
elements but it appears at the outset completely hopeless to attemp t
t o explain anything at all of the special properties of hydrogen
still less its line spectrum on the basis of considerations relating
t o such a Simple system
L et us assume for the sake of brevity that the mass of the nucle u s
is innitely large in proportion to that of the electron and that the
velocity of the electron is very small in comparison with that of
light If we now temporarily disregard the energy radiation which
according to the ordinary electrodynamics will accompany the a c
the latter in accordance with
c e l e r a t e d motion of the electron
K epler s r st law will describe an ellipse with the nucleus i n on e
of the foci
D enoting the frequency o f revolution by w and th e
maj or axis of the ellipse by 2a we nd that
.

2W

a)

7r e

2a =

4
( )

ON THE S PE C T RU M OF HYDROG E N

where e is the charge of the electron and m its mass while W is

the work which must be added to the system in order t o remove
the electron to an innite distance from the nucleus
These expressions are extre mely simple and they Show that the
magnitude of the frequency of revolution as well as the length of
the maj or axis depend only on W and are independent o f the
excentricity of the orbit By varying W we may O btain all possible
values for a) and 2a This condition shows however that it is not
possible to employ the above formulae directly in calculating the
orbit of the electro n in a hydr ogen atom F or this it will be necessary
to assume that the orbit o f the electron can n ot take on all values
and in any event the line spectrum clearly indicates that the
oscillations of the electron cannot vary continuously between wide
limits The impossibility of making any progress with a Simple
system like the one considered here might have been foretold from
a consideration o f the dimensions involved ; for with the aid of e
and m alone it is impossible to obtain a quan t ity which can be
interpreted as a diameter o f an atom or as a frequency
If we attempt to account for the radiation of energy in the manner
required by the ordinary e lectrodynamics it will only make matters
worse A s a result of the radiation of energy W would continually
increas e and the above expressions (4 ) Show th a t at the same time
the frequency of revolution of the system would increase and the
dimensions of the orbit decrease This process would not stop until
the particles had approached s o closely to one anoth e r that they no
longer attracted each other The quantity of energy which wo u ld
be radiated away before this happened would be very great If we
were to treat these particles as geometrical points this energy would
be innitely great and with the dimensio n s of the electrons as
calculated from their mass ( about
and of the nucleus as
calculated by Rutherford (about
this energy would be
many times greater than the energy changes with which we are
familiar in ordina ry atomic processes
It can be seen that it is impossible to employ Rutherford s atomic
model s o long as we conne ourselves exclusively to the ordinary
electrodynamics But this is nothing more than might have been
expected A s I have mentioned we may consider it to be an
established fact that it i s impossible to obtain a satisfac tory
,

ON THE S P E C TRU M OF HYDROG E N

10

explanation of the experiments on temperature radiation with th e

aid of electrodynamics no matter what atomic model be em
ployed The fact that the d ecl e n ci e s of the atomic model we are
considering stand out s o plainly is therefore perhaps no serious
drawback ; even though the defects of other atomic models are
much better conce a led they must nevertheless be present and w ill
b e j ust as serious
,

a n t u m t h e o r y o f s p e c tr a
u
L
et
us
now
try
to
overcome
these
Q
difculties by applying P lanck s theory to the problem
It is readily seen that there can be no question of a direct a ppl i
cation of P lanck s theory This theory is concerned with the emission
and absorption of energy in a system of electrical particles which
oscil late with a given frequency per second dependent only on the
nature of the system and independent of the amount of energy
contained in the system In a system consisting of an electron and
a nucleus the period of oscillation corresponds to the period of
revolution of the electron But the formula (4) for a) shows that the
frequency of revolution depends upon W i e on the energy of the
system S till the fact that we can not immed i ately apply P lanck s
theory to our problem is not as serious as it might seem to be for
in assuming P lanck s theory we have manifestly acknowledged the
inadequacy of the ordinary electrodynamics and have denitely
parted with the coherent group of ideas on which the latter theo ry
is based In fact in taking such a step we can not expect that all
cases of disagreement between the theoretical conceptions hitherto
employed a nd experiment will be removed by the u s e of P lanck s
assumption regardin g the quantu m of the energy momentarily
present in an oscillati ng system We stand here almost entirely on
virgin ground and upon introducing new assumptions we need only
take care not to get into contradiction with experiment Time will
have to Show to what extent this can be avoided ; but the safest
way is of course to make as fe w assumptions as possible
With this in mind let us rst examine the experiments on
temperature radiation The subj ect of direct observation is the
distribution of radiant energy over oscillations of the various wave
lengths E ven though we may assume that this energy comes from
systems of oscillating particles we kn ow little or nothing about
.

ON THE S P E C T RUM

or

HYDROG E N

11

these systems N 0 one has ever seen a P lanck s resonator n or

indeed even measured its frequency of oscillation ; we can observe
only the period of oscillation of the radiation which is emitted It
is therefore very convenient that i t is possible to show that to
obtai n the laws of temperature radiation it i s n ot necessary to
make any assumptions about the systems which emit the radiation
except that the amount of en ergy emitted each time shall be equal
to b y where h is P lanck s constant and v is the frequency of the
radiation Indeed it is possible to derive P lanck s law of radiation
from this assumption alone as shown by D ebye who employed a
method which is a combination of that of P lanck and of Jeans
Before considering any further the nature of the oscillating systems
let u s s e e whether it is possi b le to bring this assumption ab out the
emission of radiation into agreement with the spectral laws
I f the spectrum of some element contains a spectral line corre
to
the
frequency
it
will
be
assumed
that
on e of the
s ondi n
1
p
g
atoms of the element ( or some other elementary system ) can emit
an amount of energy hv D enoting the energy of the atom before
and after the emission O f the radiation by R and E we have
,

hv = E ,

0r

5
( )

D uring

the emission of the radiation the system may be regarded

as passing from one state to another ; in order to introduce a name

for these states we shall call the m

stationary states simply
indicating thereby that they form some kind of waiting places
between which occurs the emission of the energy corresponding to
the various spectral l i nes A s previously mentioned the spectrum
of an elemen t consists of a series o f lines whose wave lengths may
be expressed by the formula
By comparing this expression

with the relation given above it is seen that Since

where

X
i s the veloci ty of ligh t each of the spectral lines may be regarded
as being emitted by the transition of a system between t wo stationary
states in which the energy apart from an additive arbitrary
constant is given by chF
and
respectively U sing
this interpre tation the combination principle asserts that a series
of stationary states exists for the given system and that it can
,

'

ON

12

T HE S P E C TRU M OF HYDR O G E N

pass from on e to any other of these states with the emission of

a monochromatic radiation We s ee therefore that with a Simple
extension of our rst assumption it is possible to give a formal
explanation of the most general law of line spectra
,

H y d r o ge n

m
e
tr
u
This result encourages us to make an
c
p
attempt to obtain a clear conception of the stationary states which
have so far only bee n regarded as formal With this end in View
we naturally turn to the spectrum of hydrogen The formula
applying to this spectrum is given by the expression
s

2
712

A ccording to our assumption this spectrum is produced by tran

s i t i on s between a series of stationary states of a system concerning
which we can for the present only s a y tha t the energy of the syste m
in the nt h state apart from an additiv e constant is given by
,

Rho
n

L et

us now try to nd a connection b etween this and the

model of the hydrogen atom We assume that in the calcu lation

of the frequency of revolution of the electron in the stationary stat e s
o f the atom it will be possible to employ the above formula for a)
I t is quite natural to make this assumption ; since in trying t o
form a reasonable conception of the statio nary states there is for
the present at least no other means available besides the ordinary
mechanics
C orresponding to the nth stationary state in form u la (4 ) for w
.

let us by way

of

:
i

I /0

experiment put W :
2 B k
i

This gives us

6
( )

mm

The radiation of light corresponding to a particular spectral line

is according t o ou r assumption emitte d by a transition between
two stationary states corresponding to two di fferent frequencies of
revolution and we are not j us tied in expecting any simple r e
lation between these frequencies of revolution of th e electron and
the frequency of the emitted radia t ion Y ou understand of course
that I am by no means trying to give what might ordinarily be
described as an explanation ; no thing has been said here about
,

ON T HE S PE C T RU M OF HYDR O G E N

13

or why the radiation is emitted O n one point however we

may expect a connection with the ordinary conceptions ; namely
that it will be possible to calculate the emission of slow electro
magnetic oscillations on the basis of the classical electrodyn amics
This assumption is very strongly supported by the result of
Lor en t z s calculations which have already been described F rom
the formula for a) it is seen that the frequency O f revolution de
h ow

creases as

71

increases and that the expressio n

,

wn

n +1

approaches the

value 1
A ccording to what has been said above the frequency of the
radiation corresponding to the transition between the ( n + 1)th
a nd the nt h stationary state is give n by
.

R0

72

If

is

v e ry large this expression is approximately equal to

v

2Rc/n

3
.

In ord e r to obtain a connection with the ordinary electrodyn a mics

let us now place this frequency equal t o t he frequ ency of r e vol u
tion that is
(o
2Rc/n
I n troducing this value of ca in ( 6 ) we s ee that n disappears from
th e eq u ation and further that the e q u a t l on W l ll b e satised o nly if
,

27

6 771

The constant R is very accurately known and is as I have said

b efore equal to 10 9 6 7 5 By introducing the most recent values
for e m and h the expression on the right han d Side of the equa
tion becomes equal to
10
The agreement is as good as
c ould be expected considering the uncertainty in the exp e rimenta l
determination of the constants e m and h The agreement between
ou r calc u lations a nd the classical e lectrodynamics i s
therefore
fully as good as we are j ustied in expecting
We can not expect t o O btain a corresponding explanation of the
frequency values of the o ther stationary states C ertain simple
formal relations apply however to all the stationary States By
introducing the expression which has been found for R we
get for the nth state W = % nhw
This equation is e ntirely
,

n.

ON T HE S P E CT RU M OF HYDROG E N

14

analogous to P lanck s assumption concerning th e energy of a

resonator W in our system is readily shown to be equal to the
average value of the kinetic energy of the electron during a
single revolution The energy of a resonator was Shown by P lanck
ou may remember to be always equal to n h
F
urther
the
average
y
value of the kinetic energy of P lanck s resonator is equal to its
potential energy s o tha t the average value of the kinetic energy
is equal to nhw This
of the resonator according to P lanck
analogy suggests another manner of presenting the theory and i t
was j ust in this way that I was originally led into these con
siderations When we consider how differently the equation i s
employed here and i n P lanck s theory it appears to me misleading
to use this analogy as a foundation and in the account I have
given I have tried to free myself as much as possible from it
L et us continue with the elucidation of the calculations and in
the expression for 2a introduce the value of W which correspond s
to the nth stationary state This gives us
.

v.

2a

72

Ch

2w m 6
2

= n2

(8 )

I t is seen that for small values of n we O btain val ues for the
maj or axis of the orbit of the electron which are of the same
order of magnitude as the val u es of the diameters of the atoms
calculated from the kinetic theory of gases For large values of
n 2a becomes v
ery large in proportion to the calculated dimensions
of the atoms This however does not necessarily disagree with
experiment U nder ordinary circumstances a hydrogen ato m will
probably exist only in the state corresponding to n = 1 F or this
state W will have its greatest value and consequently the atom
will have emitted the largest amount of energy possible ; this will
therefore represent the most stable state of the atom from which
the system can not be transferred except by adding energy to it
from without The large values for 2a corresponding to large n ne e d
not therefore be contrary to experiment ; indeed we may in these
large values seek an explanation of the fact that in the laboratory
it has hitherto not b een possible to observe the hydrogen lines
corresponding to large values of n in B a lm er s formula while they
have been observed in the spec tra of certain stars In order that
the large orbits of the electrons may not b e disturb ed by electrical
,

ON

T HE S P EC T RU M OF HYDR OG E N

15

forces from the neighbouring atoms the pressure will have to be

v e ry low s o l ow indeed that it is impossible to obtain sufcient
light from a ! eissler t u be of ordinary dimensions I n the stars
however we may assume that we have to do with hydrogen which
is exceedingly attenuated and distri b uted throughout an enor
m ous ly large region of space
,

Th e P i c k e r i n g l i n e s

Y ou

have probably noticed that we have

not mentioned at all the spectrum found in certain stars which
a ccording to the opinion t hen current was assigned to hydrogen
and together with the ordinary hydrogen spectru m was considered
by Rydberg to form a connected syste m of lines completely
analogous to the Spectra of other elements Y ou have probably
also perceived that difculties would arise in interpreting this
s pectrum by means of the assumptions which have bee n employed
If such an attempt were t o be made it would be necessary to give
up the Simple considerations which lead to the expression ( 7 ) for
the constant R We shall s ee however that it appears possible t o
L et us
e xplain the occurrence of this spec trum in another way
s uppose that it is n ot due to hydrogen but t o some other simple
system consisting of a Single electron revolving about a n u cleus
with an electrical ch a rge N e The expr e ssion for w becomes then
.

C0

2 4

6 717

Repeating

the same calculations as before only in the inverse

order we nd that this system will emit a line Spectrum given by
t h e expression
,

2w N

ch

2 4

,
n2

12

(9 )

By comparing this form u la with th e formula for P ickering s and

Rydberg s series we s ee that the observed lines can be explained
on the basis of the theory if it be assumed that the spectrum is
due to an electron revolving about a nucleus with a charge 26 or
according to Rutherford s theory around the nucleus of a helium
atom The fact that the spectrum in question is n ot observed in
an ordinary helium tube but only in stars ma y b e account e d for

ON THE S P E C TRU M OF HYDR O GE N

16

by the high degree of ionization which is required for the produc

tion of this spectrum ; a neutral helium atom contains of course
t w o electrons while the system under consideration contains
only on e
The s e conclusions appear to be supported by experiment
F o w ler a s I have mentioned has recently succeeded in o b serving
P ickering s and Rydberg s lines in a laboratory experiment By
passing a very heavy current through a mixture of hydrogen and
helium F owler observed not only these lines but also a new serie s
This new series was of the same general type the wave
of lines
le n gth b eing given approximately by
.

ar

F owl e r interpreted all the observed lines as the hydrogen spectrum

sought for With the observation of the latter series of lines
however the basis of the analogy between the hypothetical
hydrogen spectrum and the other spectra disappeared and thereby
also the foundation upon which Rydberg had founded his conclu
sions ; on the contrary it is seen that the occurrence of the lines
was exactly what was t o be expected on ou r v iew
In the following table the rst column contains the wave
lengths measured by F owler while the second contains the limiting
in the third
v alues of the experimental errors given by him ;
column we nd the products of the wave lengths by the quantity
.

the values employed

pa rentheses in the last column
108

Li mi t

of e r r or

721

and

00 5

n12

72 2
2

227 7 9 0

27 3 3 3 4

227 7 7 8

25 1

227 7 8 3

23 8 5 4 7

227 7 7 9

23 0 6 2 0

227 7 7 3

225 28 8

227 7 9 1

5 410 5

10
'

4 200 3

227 7 4
227 7 7

4541 3
'

05

n,

are enclosed i n

227 7 9 1

46 8 5 9 8

3 203 3 0

for

227 8 1

10

10

(3
(3
3
(

4)
:
:
5)
:
6)

(3

:
9)

:
7)
9)
(4 :

4
(

17

ON T HE S P E C T RU M OF HYDROG E N

The values of the products are seen to be very nearly equal

while the deviations are of the same order of m agnitude as the
limits of experimental error The valu e of the product

"

(E

should for this spectrum according to the formula

be exactly
the
corresponding
produc
t
for
the
hydrogen
spectrum
F
rom
f
o
i
the tables on pages I and 16 we nd for these products 9 115 3
and 227 7 9 and dividing the former by the lat ter we get 4 0 0 16
This value is very nearly equal to 4 ; the deviation is however
much greater than can be accounted for in any way by the errors
It has been easy ho w e ver to nd a theo
of the experiments
In all the foregoing calculation s
r e ti ca l explanation of this point
we have assumed that the mass of the nucleus is innitely great
compared to that of the electron This is of course n ot th e
ca se even though it holds to a very close approximation ; for a
hydrogen atom the ratio of the mass of the nucleus to that of th e
electron will be about 18 5 0 and for a heli u m atom four times a s
great
If we consider a system consisting of an electron revolving about
a nucleus with a charge N e and a mass M we nd the following
expression for the frequency of revolution of the syste m :
,

60

W (M

m)

Mm

2 4

F rom this formula we nd in a manner quit e similar to that

previously employed that the system will emit a lin e spectrum
the wave lengths of which are given by the formula
1

27 1 N

ch

'

mM

2 4

M
(

m)

1
0
( )

If with the aid of this formula we try to nd the ratio of the

product for the hydrogen spectru m to that of the hypothetical
helium spec trum we get the value 4 0 0 16 3 which is in complete
agreement with the preceding value calculated from the e x p e r i
mental observations
I must further mention that E vans has made some exp e riments
to determine whether the spectrum in question is due to hydrogen
or helium
H e succeeded in observing on e of the lines in very
.

18

ON T HE S P E C TRU M OF HYDROG E N

p ure helium ; there was at any rate not enough hydrogen present
t o en a ble the hydrogen l ines to be observed
S ince in any e v en t
F owler does not seem to consider such evidence as conclusive it is
to be hoped that these experiments will be continued There is
however also another possibility of deciding this ques tion A s i s
evi d ent from the formula
the helium spectrum u nder con
sideration should contain besides the lines observed by F owler a
s e ries of lines lying close to the ordinary hydrogen lines These
lines may be obtained by putting
n
6 8 10 etc E ven
if these lines were present it would be extremely di fcult to
obs e rve them on account of their position with regard to the
hydrogen lines but should they be observed this would probably
also settle the question of the origin of the spectrum since no
rea son would seem t o be left to assume the spectrum to be due to
hydrogen
,

e
tr
the
spectra
of
other
ele
m
ents
the
problem
c
F
o
r
a
p
be comes more complicated since the ato m s contain a larger
n u mber of electrons It has not yet been possible on the basis of
this theory to explain any other spectra besides those which I
have already mentioned O n the other hand it ought to be
mentioned that the general laws applying t o the spectra are very
simply i nterpreted on the basis of ou r ass u mptions S O far as the
combination principle is concerned its explanation is obvious In
the m e thod we have employed our point of departure w a s largely
determined by this particul a r principle B u t a simple explanation
can be also given o f the other general law namely the occurrence
L et us assume
of Rydberg s constant in all spectral formulae
that the spectra under consideration like the spectrum of hydroge n
a r e emitted by a neutral system and that they are produced by
the b inding of an electro n previously removed from the system
If s uch an electron revolves about the nucleus in an orbit which
is large in propor tion to that of the other electrons it will be
subj e cted to forces much the same as the electron in a hydrogen
atom since the inner electrons individually will approximately
neutralize the e ffect of a part of the positive charge of the nucleus
We may therefore assume that for this system there will exist a
s e ri e s of station a ry states in which the motion of the outermost
O th e r

ON T HE S P E C T RU M OF HYDR O G E N

19

electron is approximately the same as in the stationary states of a

hydrogen atom I shall not discuss these matters any fu rther
but shall only mention that they lead to the conclusion tha t
Rydberg s constant is not exactly the same for all elements
The expression for this constant will in fact contain the factor
.

where M is the

m ass

of the n u cleus

The correction is

exceedingly small for elements of large atomic w e ight but for

h ydrogen it is from t h e point of view of spectrum analysis very
considerable If the procedure employed leads to correct results it
is not therefore permissible to calculate Rydberg s constant directly
from the h y drogen spectrum ; t h e value of the universal constant
should according to the theory be 10 9 7 3 5 and not 10 9 6 7 5
I Shall not tire you any further with more details ; I hope to
return to these ques tions here i n the P hysical S ocie t y and to
Sho w how on the basis of the underlying ideas it is possible
to develop a theory for the structure of atoms and molecules
Before closing I only wish to s a y that I hope I have expressed
myself su fciently clearly s o that you have appreciated the extent
to which these considerations conict with the admirably coherent
gro u p of conceptions which have been rightly termed the classica l
theory of electrodynamics O n the other hand by emphasizing
this con flict I have tried to convey to you the impression that it
may be also possible in the course of time to discover a certain
coherence in the new ideas
,

ES S AY 11

TH E

ON

S P E C T RA O F T H E

S E R I ES
I

E L E ME N TS

I N T RO D U C T I ON

The subj ect on which I have the honour t o speak here at the
kind invitation of the C ouncil of your soci e ty is very extensive and
it would be impossible in a single address to give a comprehensive
survey of even the most important results obtained in the theory
In what follows I shall try merely to emphasize some
o f spectra
poin ts of view which seem to me important when considering the
present state of the theory of spectra a nd the possibilities of its
d evelopme n t in the near fut u re I regret in this co nnection not to
have time to describe the history of the development of s pectral
theories although this would be of interest for ou r purpose N o
d i fc u l ty h ow e v e r in understanding this lecture need be experienced
on this account
Since the points of View underlying previous
attempts to explain the spectra differ fundamentally from those upon
which the following considerations rest This difference exists both
in the development of our ideas about the structure of the atom
and in the manner in which these ideas are used in explaining the
spectra
We shall assume accordin g to Rutherford s theory that an atom
consists of a positively charged nucleus with a number of electrons
revolving about it A ltho u gh the nucleus is assumed to be very
small in propor tion to the size of t he whole atom it will contain
nearly the e ntire mas s of th e atom I shall not state the reasons
which led to the establishment of this nu cl ea r theor y of the a tom
nor describe the very strong support which this theory has received
from very di fferent so u rces I shall mention only that result
which lends such charm and simplicity to the modern development
I refer to the idea that the number of elec
o f the atomic theory
trons i n a neutral atom is exactly e qual to the number giving th e

position of the element i n the periodic table the s o called atomic

number This assump t ion which was rst proposed by v a n den

Broek immediately suggests the possibility ultimately of deriving
A dd r e s s d eliver e d be fore th e Ph y s i ca l S oc i e ty i n B erli n A p r il 27 19 20
,

ON T HE SE R I ES S P E C T RA OF T HE E L EM EN T S

21

the explanation of the physical and chemical properties of the

elements from their atomic numbers If howeve r an explanation
o f this kind is attempted on the basis of the classical laws of
mechanics and electrodynamics insurmountable di fculties are e n
countered These di fculties become especially apparent when we
consider the spectra of the elements In fact the di fculties are
here s o obvious that it would be a waste of time to discuss them in
detail It is evident that systems like the n uclear atom if based
upon the usual mechanical and electrodyn amical con ceptions
would not even possess sufcient stability to give a spectrum con
sisting of sharp lines
In this lecture I shall use the ideas of the quantum theory It
will not be necessary par ticularly here in Berlin to consider in
detail how P lanck s fundamental work on temperature radiation
has given rise to this theory according to which the laws governin g
atomic processes exhibit a denite element of discontinuity I shall
m e ntion only P lanck s chief res u lt about the properties of an ex

oscillator
c e e d i ngly Simple kind of atomic system the P lanck
This consists of an electrically charged particle which can execute
harmonic oscillat ions about its position of equilibrium with a fr e
quen oy independent of the amplitude By studying the statistical
equilibrium of a number of such systems in a eld of radiation
P lanck was led to the conclusion that th e emission and absorption
of radiation take place in such a manner t h a t s o far as a statistical
equilibrium is concerned only certain distinctive states of the
oscillator are to be taken into consideration In these states th e
energy of the system is equal to a whole multiple of a s o called

energy quantum which was found to be proportional to the fr o

quenoy of the oscillator The particu lar energy val u es are therefore
given by the well known formula
.

En

nhw ,

where n is a whole number a) the frequency of vibra tion of the

oscillator and h is P lanck s constant
If we attempt to use this res u l t to explain th e spectra of the
elements however we encounter difculties because the motion of
the particles in the atom in spite of its simple structure is in general
e xceedingly complicated compared with the motion of a P lanck
,

ON T HE SE R I ES S P E C T RA OF T HE E L EME NT S

22

oscillator The question then arises h ow P lanck s result ought to

be generalized in ord er to make i t s application possible D i fferent
points of view immediately suggest themselves Thus we might
regard this equation as a relation expressing certain characteristic
properties of the distinctive motions O f an atomic system and try
to obtain the general form of these properties O n the other hand
we may also regard equation ( 1) as a statement ab out a property
of the process of radiation and inquire into the general laws which
control this process
In P lanck s theory it is taken for granted that the fre quency of
the radiation emitted and absorbed by the oscillator is equal to its
ow n frequency an assumption which may be written
.

2
( )

a) ,

I
I

if in order to make a sharp distinction between the frequency of

the emitted radiation and the frequency of the particles in the atoms
we here and in the following denote th e former by v and the latter
by m We s e e therefore that P lanck s result may be interpreted to
mean that the osci l lator can emit and absorb radiation only in

radiation quanta of magnitude

,

A E = hv

3
( )

I t is well kn own that ideas of this kind led E instein to a theory

of the photoelectric e ffect
This is of great importance Since it
represents the rst instan ce in which the q u antum theory was
applied to a phenomenon of non statistical character I shall n ot

here discuss the familiar difculties to which the hypothesis O f

light quanta leads in connection with the phenomena of inter
fer e nce for th e explanation of which the classical theory of radiation
has Shown itself to be s o remarkably suited A bove all I shall not
consider the problem of the nature o f radiation I shall only attempt
to Show how it has been possible in a purely formal manner t o
d e velop a spectral theory the essential elements of which may be
considered as a simultaneous rational development of the t w o ways
o f interpreting P lanck s result
.

ON T HE SE R I ES S P E C T RA OF T HE E L EME N T S
11

! E N ERAL P RI N C I P L E S O F T HE

QUAN T U M

O F S P ECT RA

23

T HE O R Y

In order to explain the appearance of line spectra we are c om

e ll e d to assume that the emission of radiation by an atomic system
p
takes place in such a manner that it is n ot possible to follow the
emission in detail by m eans Of the usual conceptions Indeed these
do not even o ffer us the means of calculating the frequency of the
emitted radiation We shall s e e however that it is possible t o gi ve
a very Simple explanation of t he general empirical laws for the
frequencies of the spectral lines if for each emission of ra diation
by the ato m we assume the fundamenta l law to hold that durin g
the entire period of the emission the radiation possesses on e a nd
the same frequency connected with the total energy emitt e d by
the fr equ ency r ela ti on
.

H ere E and E represent th e energy of the system b e for e and

after the emission
If this law is assumed the spectra do not give u s information
about the motion of the particles in t h e atom as i s s u pposed in the
usual theory of radiation but only a knowledge of the energy
changes in the various processes which can occur in the atom
F rom this point of view the spectra Show the existence of certain
denite energy values corresponding to certain distinctiv e states
o f the atoms
These states will be called the s ta ti ona r y s ta tes of
the atoms since we shall assume that the atom can remain a ni te
time in each state and can leave this state only by a process of
transition to another st ationary s t ate N otwithstanding the funda
mental departure from the ordinary mechanical and electrodynamical
conceptions we shall s e e however that it is possible to giv e a
rational interpretation of the evidence provided by the spectra on
the basis o f these ideas
A lthough we mus t assume that the ordinary mechanics can not
be used to describe the transitions between the stationary stat e s
nevertheless it has been found possible t o develop a consistent
theory on the assumption that the motion in t h ese states can be
described by the u s e of the ordinary mechanics Moreover although
the process of radiation can not be described on th e basis of the

24

ON

T H E S E R I E S SP E C TR A

THE

OF

E LEME N T S

ordinary theory of electrodynamics according to which the nat u re

of the radiation emitted by an atom is directly related to the har
monic components occurring in the motion of the system there is
found never theless to exist a far reaching cor r esp ondence between
the various types of possible transitions between the stationary
states on the on e hand and the various harmonic components o f the
motion on the other hand This correspondence is of such a nature
that the present theory of spectra is in a certain sense to be regarded
as a rational generalization of the ordinary theory o f radiation
,

H y d r o ge n

e c tr um In order that the principal points may

stand out as clearly as possible I shall before considering the more
complicated types o f series spectra rst consider the simplest spec
trum namely the series spectru m of hydrogen This Spectrum
consists of a nu mb er of lines whose frequencies are given with great
e xactness by B a lm er s form u la
sp

f
( r

5
( )

where K i s a constant and n and n are whole n umbers If we put

we get the well kno w n

n : 2 and give to n the values 3 4 etc
1 or n
Balmer series of hydrogen If we put 72
3 we obtain
respectively the ultra violet and infra red series We shall assume
the hydrogen atom simply to consist of a positively charged nucleus
with a single electron revolving about it F or the sake of simplicity
we shall suppose the mass of the nucleus to be innite in comparison
with the mass of the electron and further we shall disregard the
s mall v a ri a t l ons in the motion due to the change in mass o f the
electron with its v e locity With these Simplications the electron
will describe a closed elliptical orbit with the nucleus at one of th e
foci The frequency of revolution to and the maj or axis 2a of the
orbit will be connected with the energy of the system by the fol
lowing equations :
2W
e

"

"

7 1 6 777.

H ere e is the charge of the electron a nd m its mass while Wi s the

w ork required to remove the electron to inni t y
The Simplicity of these formulae suggests the possibility of using
them in a n at te mpt to explain the spectrum of hydrogen This
,

ON

THE SE R I ES S P E C TRA OF T HE E L EME N T S

25

ho wever is not possible s o long as we use the classical theory of

radiation It would not even be possible to understand h o w hydrogen
could emit a spectrum consisting of sharp lines ; for since a) vari e s
with W the frequency of the emitted radiation would vary con
t i nu ou s ly during the emission We can avoid these di fculties if
we use the ideas of the quantum theory I f for each line we form
the product hv by multi plying both sides of ( 5 ) by h then since
the right hand side of the resulting relation may be written as
the d i fference of two simple expressions we are led by comparison
with formula ( 4 ) to the assumption that the separate lines of the
spectrum w ill be emitted by transitions bet w een two stationary
states forming members of an innite series Of states in which the
e n ergy in the n th state apart from an arbitrary additive constant is
d etermined by the expression
Kh
,

En

The negative Sign has been chosen because the energy of the atom
will be most simply characterized by the work W required to remove
the electron completely from the atom If we now substitute
.

Kh
2

for W in formula
we O btain the following e x pression for the fr e
quen oy and the maj or axis in the n th stationary state :
( on

2h K

2a n

71 6

hK

A comparison bet ween the motions de t erm i ned by these equations

a nd the distinctive s t ates of a P lanck resonator may be Shown to
o ffer a theoretical determination of the constant K Instead of
doing this I shall show how the value of K can be found by a simple
compariso n of the spectrum emitted w ith the motion in the stationary
states a comparison which at the same time will lead us to th e
principle of correspondence
We have assumed that each hydrogen line is the result of a
transition bet ween t w o stationary states of the ato m corresponding
to different values of n E quations ( 8 ) Show that the frequency of
revolution and the maj or axis of the orbit can be entirely different
in the t w o states Since as the energy decreases the maj or axis of
the orbit becomes smaller and the frequency of revolution increases
.

ON THE SE R I ES S P E C TR A OF T HE E LEMEN T S

26

In general therefore it will be impossible to O btain a relation b e

tween th e frequency of re v olution of the electrons and the frequency
o f the radiation as in the ordinary theory of radiation
If however
we consider the ratio of the frequencies of revolution in t w o stationary
states corresponding to given values of n and n we s e e that this
ratio approaches unity as n and n gradually increase if a t the

same time the di fference n n remains unchanged By consider

ing transitions corresponding to large values of n and n we may
therefore hope to establish a certain connection with the ordinary
theory For the frequency of the radiation emitted by a transition
we get according to ( 5 )
,

"

"

"

K
I!

u
or

( r
n

'

"

9
( )

or o r

If now the num b ers n and n are large in proportion to their di ffer
ence we s ee that by equations ( 8 ) this expression may be written
approximately

"

I)

'

1
0
( )

to

where a) represen t s the frequency of revolution in the one or the

other of the two stationary states S ince n n is a whole number

we s e e that the rst part o f this expression i e ( n n a) is the

same as the frequency of one of the harmonic components into
which the elliptical motio n may be decomposed This involves the
well known result that for a system of particles having a periodic
motion of frequency w the displacement f of the particles in a given
direction in space may be represented as a function of the time by
a tri gonometri c series of the form

20

C OS

27 7

'

m
t
(

1
1
( )

where the summation is to be extended over all positive integral

values of 7
We s e e therefore that the frequency of the radiation emitted
by a transition between two stationary states for which the numbers
n and n are large in proportion to their di fference will coincide
with the frequency of one of t he components of the radiation which
according to the ord inary ideas of radiation would be expected from
the motion of the atom in these states provided the last factor on
,

O N TH E S E R I E S SP E C TR A

TH E

OF

E L EME N T S

the right hand Side of equation ( 10 ) is equal to

which is identical to the condition
-

2W

27

This condition

12
( )

is in fact ful lled if we give to K its value as found from measure

ments on the hydrogen spectrum and if for e m and h we use the
values obtained directly from experiment This agreement cl early
gives us a connecti on betw een the sp ectr um a nd the a tomi c m odel of
hy dr og en which is as close as could reasonably be expected con
s i der i n
the
fundamental
difference
between
the
ideas
of
the
quan
g
tum theory and of the ordinary theory of radiation
,

r e s p o n d e n c e p r i n c i p l e L et us now consider somewhat

more closely this relation between the spectra on e would expect on
the basis o f the quantum theory and on the ordinary theory of
radiation The frequencies of the spectral lines calculated according
t o both methods agree completely in the region where the stationary
states deviate only little from on e another We must not forget
however that the mechanism of emission in both cases is di fferent
The di fferent frequencies corresponding to the various har monic
components of the motion are emitted Simultaneo u sly according to
the ordinary theory of radiation and with a relative intensity de
pending directly upon the ratio of the amplitudes of these oscilla
tions But according to the quantu m theory the various spectral
lines are emitted by entirely distinct processes consisting of tran
s i t i on s from one stationary state to various adj acent sta tes so that

the radiation corresponding to the 7 t h harmonic will be e mitted

by a transition for which n n

The relat i ve intensity
with which each particular line is emitted depends consequently
upon the relative probability O f the occurrence of the different
transitions
This correspondence between the fr e qu e n ci es determined by the
two methods must have a deeper signicance and we are led to
antici pate that it will also apply to the intensities This is e qu i v a
lent to the statement that when the quantum numbers are large
the relative probability of a particular transition is connected in a
simple manner with the a m plitude of the corresponding harmonic
component in the motion
Th e

c or

'

O N T HE SE R I ES S P E C T RA OF THE E LEME N TS

28

This peculiar relation suggests a

l la w

the

f
of tr a ns i ti ons betw een s ta ti on a r
s ta tes
Thus
we
shall
assume
that
y
even when the quantum numbers are small the possibility of
transition between two stationary states is connected wi t h the
presence of a certain harmonic component in the motion of the

system If the numbers n and n are not large in proportion to

their di fference the numerical value of the amplitudes of these
components in the two stationary states may be entirely di fferent
We must be prepared to nd therefore that the exact connection
between the probability of a transition and the amplitude of the
corres ponding harmonic component in the motion is in general
complicated like the connection between the frequency of the radia
tion and that of the component F rom this point of vie w for
example the green line H B of the hydrogen spectrum which cor
responds to a transition from the fo u rth to the second stationary

state may be considered in a certain sense to be an octave of th e

red line H corresponding to a transition from the third to the
second s tate even though the frequency of the rst line is by no
m eans twice as great as that of the latter In fact the transition
giving rise to H B may be regarded as due to the presence of a har
monic oscillation in the motion of the atom which is an octave
higher than the oscillation giving rise to the emission of H
Before considering other spectra where numerous opportunities
will be found to use this point of view I shall brie fly mention a n
interesting application to the P lanck oscillator If from ( 1) and
we calc u late the frequency which would correspond to a transition
between two particular states of such an oscillator we nd
ra
n
e
e
g

or

occu r r ence

'

a ,

12

'

1
3
( )

to,

where n and n are the numbers characterizing the states It was

an e ssential assumption in P lanck s theory that the frequency of
the radiation emitted and absorbed by the oscillator is always equal
to a) We see that this assumption is equivalent to the assertion
that transitions occur only between two successive stationary states
in sharp contras t to the hydrogen atom A ccording to our View
however this was exactly what might have been expected for we
must assume that the essential di fference between the oscillator
and the hydrogen atom is that the motion of the oscillator is Simple

ON

THE SE R I ES S P E C TRA OF T HE E LEME N T S

29

harmonic We can s e e that it is possible to develop a formal theory

of radiation in which the spectr u m o f hydrogen and the simple
spectrum of a P lanck oscillator appear com pletely analogous This
t heory can only be formulated by on e and the same condition for
a syste m as Simple as the oscillator In general this cond i tion
breaks up into two parts one concerning the x ation of the stationary
states and the other relating to the freque ncy of the radiation
emitted by a transition between these states
.

e n er a l s p e c tr a l l a w s A lthough the series spectra of the

elements of higher atomic number have a more complicated s tr u c
ture than the hydrogen spectrum Simple la ws have been disco vered
showing a remarkable analogy to the Balmer formula Rydberg
and Ritz Showed that the frequencies in the series Spectra of many
elements can be e x pressed by a for mula of the type
!

f
(
f

are two
where n and n are two whole numbers and fk and
functions belonging to a series of functions characteristic of the
element These functions vary in a simple manner with n and in
particular converge to zero for increasing values of n The various
series of lines are obtained fro m this formula by allowing the rst
t
term
remain
cons
ant
while
a
series
of
consecutive
whole
n
t
o
( )
A ccording
n umbers are substituted for n in the second term fk
to the Ritz com bi na ti on p r i ncip le the entire spectrum m ay then
be obtained by forming every possible combination of two values
amo n g all the quantities f! (n)
The fact that the frequency of each line of the spectrum may be
written as the di fference of two Simple expressions depending upon
w hole numbers suggests at once that the terms on the right hand
sid e multiplied by h may be placed equal to the energy in the
various stationary sta t es of the atom The existence i n the spectra
o f the other elements of a number of separate functio n s of n compels
u s to assume the presence not of one but of a number of series of
stationary states the energy o f the nt h state Of the kt h series apart
from an arbitrary additive constant being given by
V

"

14 )

'

"

'

'

1
5
( )

This complicated character of the ensemble of stationa ry states of

atoms of higher atomic nu mber is e x actly what w a s to be expected

ON T HE SE R I ES S PE C T RA OF THE E L E M E N T S

30

fro m the relation between the spectra calculated on the quant u m

theory and the decomposition of the motions of the atoms into
harmonic oscillations From this point of view we may regard the
simple character of the stationary states of th e hydrogen atom as
intimately connected with the simple periodic character of this
atom Where the neutral atom contains more than on e electron we
nd much more complicated motions with correspondingly compli
We m ust therefore expect a more
c a t e d harmonic components
complicated ensemble of stationary states if we are still to have a
correspond ing relation between the motions in the atom and the
spectrum In the course of the lecture we Shall trace this corre
s p on d e nc e in detail and we shall be led to a Simple explanation of
the apparent capricio usness in the occ urrence of lines predicted by
the combinatio n principle
The following gure gives a survey of the stationary states of
the sodium a tom ded u ced from the series terms
,

(II- l l

m
.

i a gr a m

of

th e

s e r e s S p ec t u

m of s od i u m

"

=
(k=
2)

(H )

Th e stationary states are represented by black dots whose distanc e

from the vertical l i ne a a i s proportional to the numerical value
The arrows in the gure indicate the
of the energy in the states
transitions giving those lines of the sodium spectrum which appear
under the usual conditions of excitation The arrangement of the
states in horizontal rows corresponds to the ordinary arrangement

spectral terms in the spectroscopic tables Thus the states

o f the
in the rst row
correspond to the variable term in the Sharp

series the lines of which are emitted by transitions from these

states to the rst state in the second row The states in the second
.

ON T HE SE R I ES S P E C T RA OF T HE E L EME N TS

31

correspond to the variable term in the principal series

which is emitted by transitions from these states to the rst state
in the S row The D states correspond to the variable term in the
diffuse series which like the sharp series is emitted by transitions
t o the rst state in the P row and nally the B states correspond

to the variable term in the Bergmann series ( fundamental series )

in which transitions take place to the rst state in the D row The
manner in which the various rows are arranged with reference t o
o n e another will be used to illustrate the more detailed theory
which will be discussed later The apparent capriciousness of the
combination principle which I mentioned consists in the fact that
under the usual conditions of excitation not all the lines belong i ng
to possible combinations of the terms of the sodium spectrum appear
but only those indicated in the gure by arrows
The general question of the x ation of the stationary states of
an atom containing several electrons presents di fculties of a pro
found character which are perhaps still far from completely solved
I t is possible however t o obtain an immediate insight into the
stationary states involved in the emission of the series spectra by
considering the empirical laws which have been discover e d about
the spectral terms A ccording t o the well kn own law discovered b y
Rydberg for the spectra of elements emitted under the usual con
d i t i on s of excitation the functions f! ( n ) appearing in formula ( 14 )
can be written in the form
r ow

P
( )

f},

( )
n

1
6
( )

where
represents a function which converges to unity for
large values of n K is the same constant which appears in formula
5
o
for
the
spectrum
hydrogen
This
result
must
evidently
be
f
)
(
explained by supposing the atom to be electrica lly neutral in these
states and one electron to be moving round the nucleus in an orbit
the dimensions of which are very largein proportion to the distance
o f the other electrons fro m the nucleus
We s ee indeed that in
this case the electric force acting on the outer electron will to a
rst approximation be the same as that acting upon the e lectron
in the hydrogen atom and the approximation will be the b etter
the larger the orbit
.

ON T HE SE R I ES S P E C T RA OF THE E LEM EN T S

32

O n account of the limited time I shall n ot discuss how this

explanation of the u niversal appearance of Rydberg s constant in
the arc spectra is convincingly supported by the investigation of
the spark Spectra These are emitted by the elements under the
i nuence of very strong electrical discharges and come from ionized
not neutral atoms I t is important however that I Should indicate
briey how the fundamental ideas of t he theory and the assumption
that in the states corresponding to the spectra one electron moves
in an orbit aro u nd the others are b oth s u pported by investigation s
o n selective absorption and the excitation of spectral lines by
bombardment by electrons

Ab s o r p ti o n

t a t i o n o f r a d i a t i o n Just as we have
assumed that each emission of radiation i s due to a transi t ion from
a stationary state of higher to on e of lower energy s o also we mus t
assume absorption of radiation by the atom to be due to a transition
in the opposite direction F or an element to absorb light corre
to
a
given
line
in
its
series
spectrum
it
is
therefore
s ond i n
g
p
necessary for the atom of this element to be in that on e of the two
states connected with the line possessin g the smaller energy value
If we now consider an element whose atoms in the gaseous state
d o not combine into molecules i t will be necessary to assume that
under ordinary conditions nearly all the atoms exist in that stationary
stat e in which the value of the energy is a minimum This state
I shall call the nor m a l s ta te We must therefore expect th a t th e
absorption spectrum of a monatomic gas will contain only those
lines of the series spectru m whose emission corresponds to tran
s i ti on s to the normal state
This expectation is completely conrmed
by the spectra of the alkali metals The absorption spectrum o f
sodium vapour for example exhibits lines corresponding only t o
the principal series which as mentioned in the description of the
gure corr e sponds with transitions to the state of minimum energy
F urther conrmation of this view of the process o f absorption is
given by experiments on r es ona nce r a di a ti on Wood rst sho wed
that sodiu m vapour subj ected to ligh t correspond i ng to the rs t

line of the principal series the familiar yello w line acquires the
ability o f again emitting a radiation consisting only of the light of
this lin e We ca n explain this by supposing the sodium atom to
and

ex ci

ON T HE SE R I ES

SP

E C TRA OF T HE E L EME N T S

33

have been transferred fro m the normal state to the rst state in
the second r ow The fact that the resonance radiation does not
e xhibit the same degree Of polarization as the incident light is
i n perfect agreement with our assumption tha t the radia t ion from
the excited vapour is not a resonance phenomenon in the sense of
the ordinary theory of radiation but on the contrary depends on a
process which is not directly connected with the incident radiation
The phenomenon of the resonance radiation of the yellow sodium
line is however not quite s o simple as I have indicated Since a s
you know this line is really a doublet This means that the variable
terms of the principal series are not simple but are represented by
two values slightly di fferent from one another A ccording to our
picture of the origin of the sodium spectrum this means that t he
P states in the secon d row in the gu r e as opposed to the S state s
in the rst row are not simple but that for each place in this r o w
there are two stationary states The e n ergy values di ffer s o littl e
from on e another that it is impossible to represent them in the
gure as separate dots The e mission (and absorption ) o f the two
components of the yello w line are therefore connected with two
di fferent processes This was b eautifully shown by some later r e
searches of Wood and D unoyer They found that if sodium vapour
is subj ected to radiation from only one of the two components of
the yellow line the resonance radiation at least at low pressures
consists only of this component These experiments were later
continued by S trutt and were extended to the case where the
exciting line corresponded to the second line in the principal series
S trutt found t hat the resonance radiation consisted apparently only
to a s mal l extent of light of the same frequency as the incident
light while the greater part consisted of the familiar yello w line
This result must appear very astonishing on the ordinary ideas of
resonance Since as S trutt pointed out no ra tional connection exists
between the frequencies of the rst and second lines of the principal
series I t i s however easily e x plained from ou r po i nt of view From
the gure it can be seen that when an atom has been transferred
into the second state in the second row in addition to the direct
return to the normal state there are still two other transitions
w hich may give rise to radiation namely the transitio n s to the
second state in the rst row and to the rst state in the third r ow
.

34

O N TH E

S E R I E S S PE C TRA

O F TH E

E L EME N T S

The e xperiments See m to indicate that the second of these three

transitions is most probable and I s h all Sho w later that there is
so me theoretical j ustication for this conclusion B y this transition
which results in the emission of an infra red line which could not
be obs e rved with the e x perimental arrangement the atom is taken
to the second state of the rst row and from this state only
This
on e trans ition is possible which again gives an i nfra red line
transition takes the ato m to the rst state in the second r ow and
the subsequent trans ition to the normal state then gives rise to the
y e llow line S trutt discovered another equally surprisin g result
that this yellow resonance radiation seemed to consist of both
components of the rst line of the principal series even when the
incident light consis ted of only on e component of the second line
This is in beautiful agreement with ou r
of the principal series
picture O f the phenomenon We must remember that the states in
th e rst r ow a r e simple s o when the atom has arri v ed in on e of
thes e it has lost every possibility of later giving any indication
from which of the two states in the second row it originally came
S odium vapour in addition to the absorption corresponding t o
th e lines of the principal series exhibits a s electi ve a bs orp ti on i n a
conti n u ou s sp ectr a l r egi on beginning at the limit of this series and
This conrms in a striking manner
e xtending into the ultra violet
o ur assu mption that the absorption of the lines o f the principal
series of sodium results in nal states o f the atom in which on e of
th e electrons revolves in larger and larger orbits F or we m u st
a ss u me tha t this continuous absorption corresponds to transitions
fr om the normal state to s tates in which the electron is in a position
to remove itself i nnitely far from the nucleus This phenomenon
exhibits a complete analogy with the p hotoel ectri c eect from an
il lu minated metal plate in which by using light of a suitable
frequency electrons o f any velocity can be obtained The frequency
however must always l ie above a certain limit connected according
to E instein s theory in a simple manner with the energy necessary
to bring an electron ou t of the metal
This view of the origin of the emission and absorption spectra
h as b een conrmed in a very interesting manner by e x periments
on the ex ci ta ti on o
s ectr a l li nes a nd
r od u cti on o
i
n
z a ti on b
o
i
f p
f
y
p
e l ec tr on bomba r d ment The chief advance in this eld is due to the
,

O N TH E S E R I E S S PE C TRA

O F TH E

E LEM EN T S

35

well known experiments of F ranck and H ertz These i nvestigators

obtained their rst important results from their experiments on
mercury vapour whose properties particularly facilitate such ex
O
n
account
of the great importance of the results these
er i m e n t s
p
experiments have been extended to most gases and metals that can
be O btained in a gaseous state With the aid of the g u re I shall
briey illustrate the results for the case of sodium vapour It was
found that the electrons upon colliding with the a toms were thro wn
back with undiminished velocity when their e n ergy was less tha n
that required to transfer the atom from the normal state to the
next succeeding stationary state of higher energy value In the
case of sodium vapour this m eans from the rst state in the rst
A s soon however as the
r ow to the rst state in the second r ow
energy of the electron reaches this critical value a new type of
collision takes place in which the electron loses all its kinetic
energy while at the same time the vapour is excited and emits a
radiation corresponding to the yellow l i ne This is what would b e
expected if by the collision the atom was transferred from the
normal state to the rst one in the second row For some time it
was uncertain to what extent this explanation was correct Since
in the experiments on mercury vapour it was found that together
with the occurr ence of non elastic impacts ions were always formed
i n the vapour F rom ou r gure however we would expect ions
to be produced only when the kinetic energy of the electrons is
su fciently great to bring the atom ou t of t h e normal state to the
common limit of the states L ater experiments especially by D avis
and ! oucher have settled this point I t has been Shown that ions
can only be directly produced by collisions when the kinetic energy
o f the electrons corresponds to the limit of the series and that the
ionization found at rst was an indirect e ffect a rising from the
photoelectric e ffect produced at the metal walls of the apparatus
by the radiation a rising from the ret u rn of the mercury atoms to
the normal state These experimen
ts provide a direct and inde
pendent proof of the reality of the distinctive stationary states
w hose existence we were led to infer from the series spectra
At
the same time we get a striking impression of the insufciency of
the ordinary electrodynamical and mechanical conceptions for the
description of atomic processes not only as regards the emission
3 2
-

ON T HE SE R I ES S PE C TRA OF THE E L EME N T S

36

radiation but also in such phenomena as the collision

electrons with atoms

of

of

free

III

D E VE L O P M EN T O F T HE QU AN T U M T H E O RY
O F S P E CT RA

We s e e that it is possible by making use of a few Simple ideas

to obtain a certain insight into the ori gi n of the series spectra
But when we attempt to penetrate more deeply difculties arise
In fact for systems w hich are not Simply periodic it i s not possible
to obtain su fcient information about the motions of these sys t ems
in the stationary states from the numerical values of the energy
alone ; more determining factors are required for the xation of
the motion We meet the same difculties when we try to explain
in detail the characteristic e ffect of external forces upon the spectrum
A foundation for further advances in this eld has
o f hydrogen
been made in recent years through a development of the quan tum
theory which allows a xation of the stationary states not only in
the case of simple periodic systems but also for certain classes of
non periodic systems These are the condi ti ona l ly p er i odi c s ys tems

whose equations of motion can be solved by a separation of the

variables If generalized coordi nates are used the descri ption of
the motion of these systems can be reduced to the consideration
co mpone n ts of motion E ach of these
o f a number of generalized
corresponds to the change of only on e of the coordinates and may

therefore in a certain sense be regarded as independent The

method for the xation of the stationary states consists i n xing
the motion of each of these components by a condition which can
be considered as a d i rect generalization of condition ( 1) for a
P lanck oscillator s o that the stationary states are in general
characterized by as m any whole numbers as the number of the
degrees of freedom which the system possesses A considerable
number of physicists have taken part in this development of the
quantum theory including P lanck himsel f I also wish to mention
the important contribution made by E hrenfest to this subj ect on
the limitations of the applicability of the laws of mechanics to
atomic processes The decisive advance in the application of the
quan t um theory to spectra however is due to S ommerfeld and his
followers H owever I shall not further d iscuss the systematic form
.

O N T HE SE R I ES S PE C TRA OF T HE E LEME N T S

37

in which these authors have presented their results In a paper which

appeared some time ago in the Transactions of the C openhagen
Academy I have Shown that the spectra calculated with the aid
of this method for the xation of the stationary states exhibit a
correspon dence with the spectra which should correspond to the
motion of t h e system similar to that which we have already con
s i d e r e d in the case of hydrogen
With the aid of this general
correspondence I shall try in the remainder of this lecture to
Show how it is possible to present the theory o f series spectra
a n d the effects produced by external elds of force upon these
spectra in a form which may be considered as the natural generali
This form appears to me
z a t i on of the foregoing considerations
to be especial ly suited for future work in the theory of spectra
Since it allows of an immediate insight into problems for which
the methods mentioned above fail on acco u nt of the complexity of
the motions in the atom
.

e x t e r n a l for c e s on th e h y d r oge n s p e c t r u m We
shall now proceed to investigate the e ffect of small perturbing
forces upon the spectrum o f the simple system consisting Of a Single
e lectron revolving about a nucleus For the sake of simplicity we
shall for the moment disregard the variation of the mass of the
electron with its velocity The consideration of the sm a ll chan ges
in the motion due to this variation has been of great importance
in the developm e nt of S ommerfeld s theory which originated in the
explanation of the ne s tr u ctur e of the hy dr ogen l i nes This ne
structure is due to the fact that taking into account the variation
of mass with velocity the orbit o f the electron deviates a little
from a Simple ellipse and is no longer exactly periodic This de via
tion from a Keplerian motion is however very small compared
with the perturbations due to the presence of external forces such
In atoms
a s occur in experiments on the Zeeman and S tark e ffects
o f higher atomic n umber it is also n egligible co m pared with the
disturbing e ffect of the inner el e ctrons on the motion of the outer
electron The neglect of the change in mass will therefore have no
important inuence upon the explanation of the Zeeman and S tark
e ffects or upon the explanation of the di fference bet ween th e
hydrogen spectru m and the spectra of other elements
E ffe c t

of

ON T HE SE R I ES S P E C T RA OF T HE E LE M E N T S

38

We shall therefore as before consider the motion of the u n

perturbed hydrogen atom as simply periodic and inquire in the
rst place a bout th e stationary states corresponding to this motion
The energy in these states will then be determined by expression ( 7 )
which was derived from the spectrum of hydrogen The energy of
the system being given the maj or axis of the elliptical orbit of the
electron and its frequency of revolution are also determined S ub
K
in
formulae
and
8
the
expression
for
given
in
7
s ti t uti n
( )
( )
g
we obtain for the energy maj or axis and frequency of revolution
i n the nth state of the unperturbed atom the expressions
.

1 27

1 4w

.
6 772

2a n

= n2

27r

cun

z z

i"

We must further assume that in the stationary states of the

u n perturbed system the for m of the orbit is so far undeterm i n ed
that the excentricity can vary continuously This is not only i m

f
Since the
m ediately indicated by the principle o correspondence
frequency of revolution i s determined only by the energy and not
by the excentricity but also by the fact that the presence of any
small extern al forces will in general in the course of time produce
a nite change in the position as well as in the excentricity of the
periodic orbit while in the maj or axis i t can produce only small
changes proportional to the intensity of the pertu rbing forces
In ord e r to x the stationary states of systems in the presence
of a given conservative external eld of force w e shall have t o
i nvestigate on th e basis of the principle of correspondence how
these forces affect the decomposition of the motion into harmonic
oscillations O win g to the external forces the form and position of
the orbit will vary continuously In the general case these changes
will be s o complicated that it will not be possible to decompose the
per turbed motion into discrete harmonic oscillations I n such a
case we must expect that the perturbed system will not possess
any Sharply separated stationary states A lthough each emission
of radiation must be assumed to be monochromatic and to proceed
according t o the general frequency condition we shall t herefore
expect the nal effect to be a broadening of the sharp spectral lines
In certain cases however the perturba
o f the unpert u rb ed system
.

ON T HE SE R I ES S P E C T RA

or

THE E LEMEN TS

39

tions w ill be of such a regular character that the perturbed system

can be decomposed into harmonic oscillation s altho u gh the ensemble
o f these oscillations will naturally be of a more complicated k i n d
than in the unperturbed system This happens for example whe n
the variations of the orbit with respect to t i me are periodic In
this case harmonic oscillations will appear in the motion of t he
system the frequencies of which are equal to whole multiples of the
p e riod of the orbital perturbations and in the spectrum t o b e
e x pected on the basis of the ordinary theory of rad i ation we w ould
expect components corresponding to these frequencies According
to the principle of correspondence we are therefore immediately
led to the conclusion that to each stationary state in the u np er
t u r b e d system there corresponds a number of stationary states in
the perturbed system in such a m anner that for a transition
between two of these states a radiation i s emitted whose frequency
stands in the same relationship to the periodic cours e of the
variations in the orb it as the spectrum of a simple periodic syste m
does to its motion in the stationary states
,

Th e S t a r k

e ffe c t An instructive example of the appeara nce of

periodic perturbations is obtained when hydrogen is subj ected to
the effect of a homogeneous electric eld The e xcentricity a nd
the position of the orbit vary continuously under the inuence of
D uring these changes however it is found that the
th e eld
centre of the orbit remains in a plane perpendicular to the di r e c
tion of the electric force and that its mo tion in this plan e is
simply periodic When the centre has returned to its starti ng
point the orbit will resume i t s original excentrici ty and position
and from this moment the entire cycle of orbits will be repeated
In this case the determination of the energy of the stationa ry
states of the disturbed system is extremely simple since it is found
that the period of the disturbance does not depend upo n the
original conguration of the orbit nor therefore upon th e position
of the plane in which the centre of the orbit moves b u t only upon
the maj or axis and the frequency of revolution From a simple
calculation it is found that the period 0 is given by the following
formula
.

36 F

'

8 7r m a m
2

1
8
( )

ON T HE SE RI ES S P E C T RA OF T HE E L EME N T S

40

where F i s the intensity O f the external electric eld From

analogy wi t h the xation of the distinctive energy values of a
P lanck oscillator we mus t therefore expect that the energy difference
between two different states corresponding to the same stationar y
state of the unperturbed system will Simply be equal to a whole
multiple of the product of h by the period 0 of the perturbations
We are therefore immediately led to the following expression for
the energy of the sta t ionary states of the perturbed system
.

'

E : E,

kh a ,

1
( 9)

where E depends only upon the number n characterizing the

stationary state of the unperturbed system while It is a new whole
number which in this case may be either positi v e or negative A s
we shall see below consideration of the relation between the energy
a n d the motion of the syste m shows that lo must be numerically
less than n if as before we place the quantity E equal to the
energy W of the n th stationary state of the undisturbed atom
S ubstituting th e values of Wm
and a given by ( 17 ) in formula
1
w
e
e
t
9
( )
g
n

7,

1 27 r

3h F

nk

( 20 )

To nd the e ffect of an electric eld upon the lines of the hydrogen

Spectrum we use the frequency condition ( 4 ) and obtain for th e
frequency v of the radiation emitted by a transition between tw o

stationary states dened by the numbers n k and n lo

,

27 r

3h F

( 0)
77

8 77

(
cm

n lc

It is well known that this formula provides a complete explana

tion of the S tark e ffect of the hydrogen lines I t corresponds
exactly with the one obtained by a d ifferent method by E pstein
and S chwarzschild They used the fact that the hydrogen atom in
a homogeneous electric eld is a conditionally periodic system
permitting a separation of variables by the use of parabolic c o
ordinates The stationary states were xed by applying quantum
conditions to each of these vari ables
We shall n ow consider more closely the correspondence bet w een
th e changes i n the Spectrum of hydrogen due to the presence of
.

O N T H E S E R I E S S PE C T RA

O F TH E

E L EME N T S

41

an electric eld and the decomposition of the perturbed motion

of the ato m into its harmonic components
Instead of the Simple
d ecomposition into harmonic components correspondin g to a simple
K epler motion the displacement 5 of the electron in a given
direction in space can be expressed in the present case by the
formula
.

C OS

277

'

TO)

ICO

05
.

where a) is the average frequency of revolution in the pert u rbed

orbit and a is the period of the orbital perturbation s while Cm and
c " are constants The summation is to be extended over all integral
values for 7 and lo
If we now consider a transition between two stationary states

characterized by certain numbers n 10 and n lo we nd that in

the region where these numbers are large compared with their

differences n n and !C k the frequency of the spectral line

which is e mitted will be given approximately by the formul a
,

12 N

'

"

k
(

a)

2
( 3)

'

We s e e therefore that we have obtained a relation between the

spectrum and the motion of precisely the same character as in the
simple case of the unperturbed hydrogen atom We have here a
Similar correspondence between the harmonic component in the
mo tion corresponding to denite values for 7 and lo in formula
and the transition bet w een two stationary states for which n n : 1

and k lo x
A number of interesting results can be obtained from this
correspondence by consideri n g the motion in more detail E ach
harmonic component in expression ( 22) for which 7 1c is an even
number corresponds to a linear oscillation parallel to the direction
o f the electric eld while each component for which 7 + x is odd
corresponds to an elliptical oscillation perpendicular to this d i r e c
tion The correspondence princip le suggests at once that these
facts are connected with the cha r a cter i s ti c p ola r i z a ti on observed in
the S tark e ffect We would anticipate that a transition for which
l
is
even
would
ive
rise
to
a
component
with
an
o
n
n
k
(
) (
)
g
electric vector parallel to the eld while a transition for which

n
n
is
odd
would
correspond
a
component
w
ith
an
k
k
t
o
(
) (
)
,

"

ON T HE SE R I ES S P E C TRA OF T HE E L EME N T S

42

electric vector perpendicular to the eld These results ha e been

fully conrmed by experiment and correspond to the empirical rule
o f polarization which E pstein proposed i n his rst paper on the
S tark e ffect
The applications of the correspondence principle that have s o
far been described have be en purely qualitative in character It is
possible however to obtain a quantitative estimate of the relative
intensity of the vari ous components of the S tark effect of hydrogen
by correlating the nu merical values of the coe fcients Cm in formula
2
2
o
with
the
probability
the
corresponding
transitions
between
f
( )
the stationary states This problem has been treated in detail by
Kramers in a recently published dissertation In this he gives a
thorough discussion of the appl ication of the correspondence prin
c i l e to the question of the intensity of spectral lines
p
v

Th e Z e e m a n

e ffe c t The prob lem of the effect of a homoge n eous

magnetic eld upon the hydrogen lines may be treated in an
entirely analogous manner The effect on the motion of the hy
drogen atom consists Simply of the superposition of a uniform r o
t a t i on upon the motion of the electron in the unperturbed atom
The axis of rotation is parallel with the direction of the magneti c
force while the frequency of revolution is given by the formula
.

'

4 7t m c

2
4
( )

where H is the in tensity of the eld and c the velocity of light

A gain we have a case where the perturbations are simply
periodic and where the period of the perturbations is independent
of the form and position of the orbit and in the present case even
o f the maj or axis
S imilar considerations apply therefore as in the
case of the S tark e ffect and we must expect that the energy in the
stationary states will again be given by formula
if we s ub
s t i t u t e for a
the valu e given in expression
This result is
also in complete agreement with that obtained by S ommerfeld and
D ebye The method they used involved the solution of the e quations
o f motion by the method of the separation of the v ariables
The
appropriate coordinates are polar ones about an axis parallel to
the eld
If we try however to calculate directly the e ffect of the eld by
.

'

T HE SE R I ES S PE C T RA OF T HE E L EME N T S

ON

43

means of the frequency condition

we immediately meet with
a n apparent disagreement which for so me time was regarded as a
grave di fculty for the theory A s both S o m merfeld and D ebye
have pointed ou t lines are not O bserved correspondi n g to every
transi t ion between the statio nary states included in the formula
We overcome this di fcu l ty however a s soon as we apply the
prin ciple of correspondence If we consider the harmonic com
of
the
motion
we
obtain
a
simple
explanation
both
of
the
o
n
n
e
t
s
p
n on occurrence of certain transitions and O f the observed polariza
tion In the magnetic eld each elliptic harmonic component having
the frequency 7 a) splits up into three harmonic components owing
O f these on e is rectilinear
t o the uniform rotation O f the orbit
with frequency 7 a) oscillating parallel to the magnetic eld and
oscillating in
a
t w o are circular with frequencies Ta)
0 and 7 a
opposite directions in a pl a ne perpendicular to the direction of the
eld C onsequently the motion represented by formula ( 22) contains
no components for which 1c is numerically greater than 1 in contrast
to the S tark e ffect where components corresponding to all val ues
of 1c are present
N ow formula ( 23 ) again applies for large values
of n and k
and Shows the asymptotic agreement between the
frequency of the radiation and the frequency of a harmonic com
ponent in the motion We arrive therefore at th e conclusion that
transitio n s for which 19 changes by more than unity can n ot occur
The argument is Similar to tha t by which transitions between two
distinctive states of a P lanck oscillator for which the values of n
in ( 1) di ffer by more than unity are excluded We must further
conclude that the various possible transitions consist of two types
For the on e ty pe corresponding to the rectilinear component It
remains unchanged and in the emitted radiation which possesses
the same frequency 1 as the original hy drogen line the electric
vector will oscillate parallel with the eld For the second type
corresponding to the circular components It will increase or decrease
by u nity and the radiation viewed in the direction of the eld will
be circularly polarized and have frequencies v + 0 and 1 a r e
s ec t i v e l
These
results
agree
with
those
the
familiar
L
orentz
o
f
p
y
theory The similarity in the two theories is remarkable when we
recall the fundamental difference between the ideas of the quantum
theory and the ordinary theories of radiation
.

'

'

20

20

O N T HE SE R I ES S PE C T RA OF T HE E L EME N T S

44

C e ntr a l p e r t u rb a t i o n s

An

illustration based on similar con

siderations which will thro w light upon the spectra of other ele
ments consists in nding the e ffect of a small perturbing eld of
force radially symmetrical with respect to the nucleus In this case
neither the form of the orbit nor the position of its plane will
change with time and the perturbing e ffect of the eld will simply
consist o f a uniform rotation of the maj or axis of the orbit The
perturbations are periodic s o that we may assume that to e ach
energy value of a stationary state of the unperturbed system there
belongs a series O f discrete energy values of the perturbed system
characterized by di fferent values of a whole number lo The fr e
uenc
a of the perturbations is equal to th e frequency of rotation
q
y
o f the maj or axis
F or a given law of force for the perturbing
eld we n d that 0 depe nds both on the m aj or axis and on the
excentricity The change in the energy O f the stationary states
therefore will not b e given by an e xpression as simple as th e
second ter m in formula
but will be a fu nction of k wh i ch is
di fferent for d i fferent elds It is possible however to characterize
by on e and the same condition the motion in the stationary states
of a hydrogen atom which is perturbed by any central eld
In
order to Show this w e must consider more closely the xation of
the motion of a perturbed hydrogen atom
In the stationary states of the unperturbed hydro gen atom
only the maj or axis of the orbit is to be regarded as xed
while the excentricity may assume any value S ince the change
i n the energy of the atom due to the external eld of force de
pends upon the form and position of its orbit the xation of the
energy of the atom in the presence of such a eld naturally
involves a closer determination of the orbit of the perturbed
system
C onsider for the sake of illustration the change in the hydrogen
spectrum due to the presence of homogeneous electric and mag
netic elds which was described by equation
It is found that
this energy condition can be given a simple geometrical inter
In
the
case
of an electric eld the distance from t h e
r e t a t i on
p
n ucleus to the plane in which the centre o f the orbit moves deter
mines the change i n the energy o f the system due to the presence
In the stationary states this distance i s Simply equal
of the eld
.

ON THE SE R I ES S P E C TRA OF T HE E L EME N T S

to

k
7

times half the maj or axis

of

the orbit

45
of

In the case

a mag

n etic eld it is found that the quantity which determines t h e change

of energy of the system i s the area o f the proj ection of the orbit
upon a plane perp endicular to the magnetic force In the various
.

s tationary states this area is equal to

lo

times the area

of

a circle

whose radius i s equal to half the m aj or axis of th e orbit 1n the

case of a perturbing central force the correspondence between
the spectrum and the motion which is required by the quantum
theory leads now to the Simple condition that in the stationary
states of the perturbed system the minor axis of the rotating orbit
.

is simply equal to

times the maj or axis This condition was rst

.

derived by S ommerfeld from his general theory for the determina

tion of the stationary states of a central motion It is easily Sho wn
that this xation of the value of the m inor a x is i s equivalent to
the statement that the parameter 2p of the elliptical orbit is given
by an expre ssion of e x actly the same form as that which gives t he
maj or axis 2a in the unperturbed atom The only di fference from
the expression for 2a in ( 17 ) is that n is replaced by It so that
the value of the parameter in the stationary states of the perturbed
atom is given by
.

,,

2p ),

27

2
5
( )

6 771

The frequ ency of the radiation emitted by a transition betwee n

t w o stationary states determined in this way for which n and n are
large in proportion to their di fference is given by an expression
which is the same as that in equation
if in this case to is the
frequency of revolution of the electron in the slowly rotati n g orbit
and 0 represents the frequency of rotation of the maj or axis
Before proceeding further it might be of interest to note that
this x ation of the stationary states of the hydroge n atom perturbed
by external electric and magnetic forces does not coincide in cer ta in
r espects with the theories o f S ommerfeld
E pstein and D ebye
A ccording to the theory of conditionally periodic systems the s ta
t i on a r y states for a system of three degrees of freedom will in general
be determined by three conditions and therefore in thes e theories

46

O N TH E

S E R I E S SP E C TR A

O F TH E

E L E ME N T S

each state is characterized by three whole numbers This would

mean that the stationary states of the perturbed hydrogen atom
corresponding to a certain stationary state o f the unperturbed
hydrogen atom xed by on e condition Should be subj ect to two
further conditions a n d Should therefore be characterized by t w o
new whole numbers in addition to the number n But the per
t u r b a ti on s of the K eplerian motion are Simply periodic and the
energy of the perturbed atom will therefore be xed completely
by one additional condition The introduction of a second conditio n
will add nothing further to the explanation of the phenomenon
Since with the appearance of ne w perturbing forces even if
these are too small noticeably to a ffect the observed Zeeman and
S tark e ffects the for ms of motion characterized by such a condition
may be entirely changed This is completely analogous to the
fact that the hydrogen spectrum as it is usually observed is not
noticeably a ffected by small forces even when they are large eno u gh
to pro duce a great change in the form and position of the orb it of
the electron
.

t on h y d r o ge n li n e s Before leaving the hydro

gen Spec trum 1 shall consider briey the e ffect of the variation of
the mass of the electron with its velocity In the preceding sections
1 have described how extern al elds o f force split up the hydrogen
lines into several components but it sho uld be noticed that these
results are only accurate when the perturb ations are large in com
parison with the small deviations from a pure Keplerian motio n
due to the variation of the mass of the electron with its velocity
When the variation of the mass is taken into account the motion
of the unperturbed atom will not be exactly periodic
Instead we
O btain a mo tion of precisely the same kind as that occurring i n the
hydrogen atom perturbed by a small central eld A ccording to
the correspondence principle an intimate connection is to be ex
e c t e d between the frequency of revolution of the maj or axis of the
p
orbi t and the di fference of the frequencies of the ne structure
components and the stationary states will be those orbits whose
parameters are given by expression
If we now consider the
e ffect of external forces upon the ne struct ure components of the
hydrogen lines it is necessary to keep in mind that this xation of
Rel a ti v i ty

e ffe c

O N T HE SE R I ES S P E C TRA OF T HE E L E M E N TS

47

stationary states only applies to the unperturbed hydrogen

atom and that as mentioned the orbits in these states are in
general already strongly inuenced by the presence of external
forces which are smal l compared with those with which we are
concerned in experiments on the S tark and Zeeman effects In
general the presence of such forces will lead to a great complexity
o f perturbations and the atom will no longer possess a group o f
sharply dened stationary states The ne structure components
o f a given hydrogen line will therefore become diffu se and merged
together There are ho w ever several important cases where this
does n ot happen on account of the simple character of the per
The simplest example is a hydrogen atom perturbed
t u r b a ti on s
by a ce ntral force acting from the nucleus In this case it is evident
that the motion of the system will retain its centrally symmetrical
character and that the perturbed motion will di ffer from the n u
perturbed motion only i n that the frequency of ro t ation of the maj or
axis will be di fferent for different values of this axis and of the
parameter This point is of impor tance in the theory of the
spectra of elements of higher atomic number since a s we shall s e e
the e ffect of the forces originating from the inner electrons may
to a rst approximation be compared with that of a perturbing
central eld We can not therefore expect these spectra to exhibit
a separate effect due to the variation of the mass of t he electron
o f the same kind as that found in the case o f the hydrogen lines
This variation will not give rise to a splitting up into separate
components but only to small displacements in the position of the
various lines
We obtain still another simple example in which the hydrogen
atom possesses Sharp stationary states although the change of mass
o f the electron is considered if we take an atom subj ect to a homo
e n e o u s magnetic eld
f
The
e
fect of such a eld will consist in
g
the superposition of a rotation of the entire syste m about an axis
through the nucleus and parallel with the magn etic force It follows
immediately from this result according to the principle of corre
s on d e nc e that each ne struc t ure component must be expect e d
p
to split u p into a normal Zeeman e ffect ( L orentz triplet ) Th e
problem may also be solved by means o f the theory of conditionally
periodic systems Since the equations of motion in the presence

t he

ON T HE SE R I ES S P E C T RA OF T HE E L EME NT S

48
of

a magnetic eld even when the change in the mass is con

s id e r e d
will allo w o f a separation of the variables using polar
coordinates in space This has bee n pointed ou t by S ommerfeld
a nd D ebye
A more complicated case arises when the atom is exposed to a
homogeneous electric eld which is not s o strong that the e ffect
due to the change in the mass may be neglected In this case there
is no system of coordinates by which the equations of motion can
be solved by separation of the variables and the problem therefore
can not be treated by the theory of the stationary states of con
d i ti on a lly periodic systems A closer investigation of the perturba
tions however shows them t o be of such a charac ter that the motion
o f the electrons may be decomposed into a number of separate har
monic components These fall into t w o groups for which the dirc o
tion of oscillation is either parallel with or perpendicular to the
eld A ccordin g to the principle of correspondence therefore w e
must expect that also in this case in the presence of the eld each
hydrogen lin e will consist of a number of sharp polarized compo
n ent s
In fact by means of the principles I have described it is
possible to gi v e a unique xation of the stationary states The
problem of the e ffect of a homogeneous electric eld upon the ne
structure components of the hydrogen lines has been treated in
detail from this point of View by Kramers in a paper which will
In this paper it will be shown how it appears
s oon be published
possible to predict in detail the manner in which the ne structure
o f the hydrogen lines gradually changes into the ordinary S tark
e ffect as the electric intensity increases
,

Th e o r y

er i e s s p e c tr a L et us now turn ou r attention once

more to the problem of the series spectra of elemen t s of higher
atomic number The general appearance of the Rydberg constant
i n these spectra is to be explained by assuming that the atom is
neutral and that one electron revolves in an orbit the dimensions
o f w hich are large in comparison with the distance of the inner elec
trons from the nucleus In a certain sense therefore the motion o f
the outer electron may be compared with the motion of the electro n
o f the hydrogen atom perturbed by external forces and the appear
an ce of the v a rious series in the spectra of the other elements is
of s

O N TH E S E R I E S SP E C TR A

TH E

OF

E LEME N TS

49

from this point of vie w to be regarded as analogous to the splitting

o f the hydrogen lines into components on account o f such forces
u
p
In his theory of the structure of series spectra of the type ex
h i b i t e d by the alkali metals S ommerfeld has made the assumptio n
that the orbit of the outer electron to a rst approximation pos
sesses the same character as that produced by a Simple perturbing
central eld whose intensi ty diminishes rapidly with increasing
distance from the nucle us H e xed the motion of the external
electron by means of his general theory for the xation of the
stationary states of a central motion The application of this
m ethod depends on the possibility o f sepa rating the variables i n
the equations of motion I n this manner S ommerfeld was able to
calculate a number of energy values which can be arranged in rows
j ust like the empirical spectral terms Shown in the diagram of t he
The states g r ouped together by S om
sodium spec trum ( p
merfeld in the separate rows are exactly those which were charac
t e r i z e d by on e and the same value of It in our investigation of t h e
hydrogen atom perturbed by a central force Th e states in the
r st r ow of the gure ( row S ) correspond to the value lo 1 thos e
: 2 etc
o f the second r ow
P
correspond
to
l
o
The states corre
( )
s p ond i n
to
on e and the same value o f n are connected by dotted
g
lines which are con tinued s o that their vertical asymptotes corre
s ond to the energy value of the stationary states of the hydrogen
p
atom The fact that for a constant n and increasing values of lo
the energy values approach the corresponding values for the u np er
t u r b e d hydrogen atom is immediately evident from the theory
Since the outer electron for large values of the parame ter of its
orbit remains at a great d istance from the inner system during the
whole revolution The orbi t will become almost elliptical and the
period o f rotation of the maj or axis will be very large It can be
seen therefore that the effec t of the inner syst e m on the energy
necessary to remove this electron from the atom must become less
for increasing values of 1
9
These beautiful results suggest the possibility of nding laws of
force for the perturbing central eld which would account for the
spectra observed Although S ommerfeld in this way has in fact
succeeded i n deri v ing formulae for the Spectral terms which vary
with n for a constant k in agreement with Rydberg s formulae it
.

ON

50

THE

SE R I ES S PE C TRA OF T HE E L EME N T S

n ot b een possible to explain the Simultaneou s variation with

b oth It a nd n in any actual case This is not surprising Since it is
t o be a nticipated that the e ffect of the inner electrons on the spec
tru m could n ot be accounted for in such a simple manner F urther
consideration shows that i t is necessary to consider not only the
forces which originate from the inner electrons but also to consider
t he e ffect of the presence of the outer electron upon the motion of
t he in ner electrons
Before considering th e series spectra of elements of low atomic
n u mb e r 1 shall point ou t how the occurrence or non occurrence of
cert a in transitions can be shown by the correspondence principle
t o fu rn ish convi n cing e vidence in favour of S ommerfeld s a s s u mp
tion about the orbit of the outer electron F or this purpose we
must describe the motion of the outer electron in terms of its har
monic compon e n ts This is easily performed if we assume that the
pre sence of the inner electrons Simply produces a uniform rotation
O n account of this
o f the orbit of the outer electron in its plane
rota tion the frequency of which we will denote by a two circular

T
a)
w
rotations with the periods
will appear in the
o and r
O
motion of the perturbed electron instead of each of the har monic
ellipti cal components with a period w e in the unperturbed motion
Th e decompositio n of the perturbed motion into harmonic compo
n e nts consequently will again be represented by a formula of the
type
in whi c h only such terms appear for which to is equal
1 S ince the frequency of the emitted radiation in the
to
1 or
regi ons where n and 19 are large is again given by the asymptotic
we at once deduce from the correspondence principle
form u la
th a t the only transitions which can take place are those for which
th e values o f lo di ffer by unity A glance at the gure for the sodiu m
spectrum Shows that this agrees exactly with the experimental
re sults This fact is all the more remarkable since in S ommerfeld s
th eory the a r rangement o f the energy values of the s tationary
states in rows has no special relation t o the possibility of transition
b e tw e en thes e states
has

'

'

C or r e s p o n d e n c e p r i n c i p l e a n d c o n s e r v a t i o n o f a n gul a r m o
m e ntum Besides these results the correspondence principle sug
.

g e sts that the ra diation emitted by the perturbed atom must

O N THE SE R I ES S P E C T RA OF THE E L E M E NTS

51

exhibit circular polarization O n account of the indeterminateness

of the pla n e of the orbit however this polar i zation can not b e
directly O bserved The assumption of such a polarization is a matter
of particular interest for the theory of radiation emission O n
account O f th e general correspondence b etwee n the spectrum of
an atom a n d the decomposition of its m otion into harmonic
components we are led to compare the radiation emitted d u ring
the tran sition between t w o stationary states with the radia
tion which would be emitted by a harmonically oscillating
electron on the b asis of the classical electrodynamics In par
t i c u la r the radiation emitted accord i ng to the classical theory
by an electron revolving in a circular orbit possesses an angular
momentum and the energy AE and the angular moment u m AP of
t h e radiatio n emitted during a certain time are connected by the
relation
2
AP
AE
6
( )
H ere (0 represents th e frequency of revolutio n of the e lectron
and a ccording t o the classical theory this is equal to the frequency
If we now assume that the total e nergy emitted
v of the radiation
is equal to hv we obtain for the total angular mom e nt u m of the
radiation
.

AP

277

2
7
( )

It is extremely interesting to note that this expression is equal

to the change in the angular momen tum which th e atom su ffers in
a transition where It varies by unity F or in S ommerfeld s theory
the general condition for the xation of the stationary states of a
central system which in the special case of an approximately
K eplerian motion is equivalent t o the relation
asserts that
the angular moment u m of the system must b e equal t o a whole

multiple

of

gr

condition which may b e written in

our

n otatio n
8
2
( )

We s ee therefore that this condition has obtained direct support

from a simple consideration of the conservation of angular momen
tum during the emission of the radiation I w ish to emphasize
that this equatio n is to b e regarded as a rational generalizatio n of
,

ON T HE SE R I ES S P E C T RA OF T HE E L EME N T S

52

P lanck s original statement about the distinctive states of a har

moni c oscillator It may be of interest to recall that the possible
Signicance of the angular momen tum in applications of the
quantum theory to atomic processes was rst pointed out by
N icholson on the basis of the fact that for a circular motion the
angula r momentum is simply proportional to the ratio o f the
kinetic energy to the frequency of revolution
In a previous paper which I presented to the C op e nhagen
A cademy I pointed ou t that these results conrm the conclusions
obtained by the application of the correspondence principle to
atomic systems possessing radial or axial symmetry Rub i no wi cz
h a s independently indicated the conclusions which may be obtained
directly from a consideration of conservation of angular momentum
during the radiation process In this way he ha s O btained several
of our results concerning the various types o f possible transitions
and the polarization of the emitted radiation E ven for systems
possessing radial or axial symmetry howe ver the conclusions which
we can dra w by means of the correspondence principle are of a
more detailed character than can be obtained solely from a c on
sideration of the conservation of angular momentum F or example
in the case of the hydrogen atom perturbed by a central force we
can only conclude that It can not change by more than Unity w hile
the correspondence principle requires that It shall vary by unity
for every possible transition and that its value cannot remain n u
changed Further this principle enables us not only to exclude
certain transitions as being impossible and c a n from this point of

view be considered as a selection principle

but it also enables
us to draw conclusions about the relative probabilities of the various
possible types of transitions from the values of the a mplitudes of
the harmonic components In the present case for example the
fact that the amplitu d es of those circular components which rotate
in the same sense as the electron are in general greater than the
amplitudes of those which rotate in the O pposite sense leads us to
expect that lines corresponding to transitions for which 19 decreases
by unity will in general possess greater intensity than lines during
the emission of which It increases by unity S imple considerations
like this however apply only to spectral lines corresponding to
transitions from on e and the same stationary state In other
.

ON

T HE SE R I ES S PE C TRA OF T HE E L EME N TS

53

cases when we wish to estimate the relative inten sities of two

spectral lines it is clearly necessary to take into consideration the
relative number of atoms which are present in each o f the two
stationary states from w hich the transitions start While the i n
tensity naturally can not depe nd upon the number of atoms in the
n al state it is to be noticed however that in estimating the
probabi lity of a transition between two stationary states it is necos
sary to consider the character of the motion in the nal as well as
in the initial state since the values of the amplitudes O f the com
n
e n t s o f oscillation of both states are to be regarded as decisive
o
p
for the probability
To Show how this method can be applied I shall return for a
moment to the problem which I mentioned in connectio n with
S tru tt s e x periment on the resonance radiation of sodium vapour
This i nvo lved the discussion of the relative probability of the various
possible transitions which can start fro m that state corresponding
to the secon d term in the second row of the gure on p 3 0 These
w e re transitions to the rst and second states in the rst row and
to the rst state i n the third r ow a nd the results of experiment
i ndicate as we s a w that the probability is greatest for the second
transitions These transitions correspond to those harmonic c om
on e n t s having frequencies 2w + a
and
and
it
is
seen
0
p
that only for the second transition do the amplitudes of the co rre
s on d i n g harmonic component di ffer from zero in the ini tial as
p
well as in the nal state !In the next essay the reader will nd
that the values of quantu m number n assigned in g 1 to the
various stationary states must be altered While this correction
in no way inuences the other conclusions in this essay i t involves
that the reasoning in this passage can n ot be m aintaine d !
I have shown how the correspondence between the spectrum o f
an element and the motion of the atom enables u s to understand
the limitations in the direct applicati on of the combination principle
in the prediction of spectral lines The same i d eas gi ve an imme
diate explanation of the interesting discovery made in recent y ears
by S tark and his collaborators t h at certain new s er i es of combi n a
ti on l i n es appear w ith considerable intensity when the radia ting
atoms are subj ect to a strong external electric eld This phe
n om e non is entirely analogo u s t o t h e appearance of the s o called
.

'

ON T HE SE R I ES S P E C TRA OF T HE E L EMEN T S

54

combin a ti on tones in acoustics It is due to the fact that the

perturbation of the motion will not only consist in a n effect upon
the components originally present but in addition will give rise to
n e w components
The frequencies of these new components may be
A ccordin g to the correspond
To)
n o where K is different from i 1
ence principle we must therefore expect that the electric eld will
not o n ly inuence the lines appearing under ordinary circumstances
but that it wi ll also render possible new types of transitions which

give rise to the new combination lines observed F rom an esti

mate of the amplitudes of the particular components in the initial
and nal states it has even been found possible to account for the
varying facility with which the new lines are brough t up by the
external eld
The general problem of the effect of an electric eld on the spectra
of elements o f higher atomic number di ffers essentially from th e
simple S tark e ffect of the hydrogen lines since we are here con
cerned not with the per turbation of a purely periodic system bu t
with the e ffect of the eld on a periodic motion already subj ect to
a perturbation The problem to a certain extent resembles the
e ffect of a weak electric force on the n e structure components of
the hydrogen atom In much the same way the effect of an electric
eld upon the series Spectra of the e lements may be treated directly
b y investigatin g the perturbations of the external electron A
continuation of my paper in the Transactions of the C openhagen
A cademy will soon appear in which I shall Show how this method
enables us to understand the interesting o b servations S ta rk a n d
others h a ve made in this eld
.

h
i
f
l
m
n
d
l
i
m
s
e
e
e
tr
e
u
t
u
We
that
it
has
b
een
c
a
o
h
a
i
p
possible to obtain a certain general insight into the origin of the
series spectra of a type like that of sodium The difculties e n
countered i n an attempt to give a detailed explanation of the
sp e ctrum of a particular element however become very serious
even when we consider the spectrum of helium whose neutral atom
contains only two electrons The spectrum of this element has a
simple structure in that it consists of single lines or at any rate of
double lines whose components are very close together We nd
however that the lines fall into two groups each of which can be

Th e

ON

T HE SE R I ES S P E C TRA OF THE E L EME N TS

55

described by a formula of the type

These are usually called
the ( ortho ) helium and p a r h e li u m spectra While the latter c on
sists of Simple lines the former possesses narrow dou blets The
discovery that helium as opposed to the alkali metals possesses
two complete spectra of the Rydberg type which d o not exhib it a ny
mutual combinations was s o surprising that at times there has been
a tendency to believe that helium consisted of two elements This
way ou t of the difculty is no longer open Since ther e is no room
for another element in this region of the periodic system or more
correctly expressed for an element possessing a new spectrum The
existence of the two spectra can however b e traced back to the fact
that in the stationary states corresponding to the series spectra we
have to do with a system possessing only on e inner electron and in
consequence the motion of the inner system in th e absence of the
outer electron will b e simply periodic and therefore easily perturb ed
by e x tern al forces
I n order to illustrate this point we shall have to consider more
carefully the stationary states connected with the origin of a s er i e s
spectrum We must assume that in these states on e electron re
volves in an orbit outside the nucleus and the other el e ctrons We
m ight n ow suppose that in general a number of di fferent groups of
such states might e x ist each group corresponding t o a di fferent
stationary state of the inner system consid ered by itself Furth e r
consideration Shows however that under the usual conditions of
excitation those groups have by far the greates t probability for which

state
t h e motion of the inner electrons corresponds to the norma
of the inner system i e to that stationary state having the least
energy F urther the energy required to transfer th e i nner s yst e m
from its normal state to another stationary state i s i n general very
large compared with the energy which is necessary to trans fer an
electron from the normal state of the neutral ato m to a stationa r y
orbit of greater dimensions L astly the inner system is in general
capable o f a permanent existence only in its normal state N ow
the conguration of an atomic system in its stationary states and
also in the n ormal state will in general be completely determined
We may therefore expect tha t the inner system under the inuence
of the forces arising from the presence of the outer electron can i n
the course of time su ffer only small changes For this reason we
.

O N TH E S E R I E S S PE C T RA

56

OF

THE

E L EM E N T S

must assume that the inuence of the inner system upo n the motion
of the external electron will in general be o f the same character
as the perturbations produced by a constant external eld upon
the motion of the electron in the hydrogen atom We must there
fore ex pect a spectrum consisting of an ensem ble of spectral terms
which in general for m a connected group even though in th e
absence of e x ternal perturbing forces not every combination actually
occurs The case of the helium spectrum however is quite di fferent
since here the inner syste m contains only on e electron the motion
o f which in the absence o f the external electron is Simple periodic
provided the small changes due to th e variation in the mass of the
e lec t ron with its velocity are neglected F or this reason the form of
the orbit in the stationary states of the inner system considered by
itself will not be determi n ed In other words the stability of the
orbit is s o slight even if the variation in the mass is taken into
account that small e x ternal forces are in a position to C han ge the
excentricity in the course of t ime t o a nite e x tent In this cas e
therefore it is possible to hav e several groups of stationary states
for which the energy o f the inner system is approximately the same
while the form of the orbit of th e inner electron and its position
relative to the motion of the other electrons are s o essentially
di fferent that no transitions between the states of different groups
can occur even in the presence of external forces It can be seen
that these conclusions summarize the experimental O bservations
on the helium spectra
These considerations suggest an investigation of the nature of
the perturbations in the orbit of the inner electron of the helium
atom due to the prese n ce of the e xternal electron A discussio n
o f the he lium spectrum from this point o f View has recently been
e
iven
by
L
and
The
results
this
work
are
of
great
interest
par
o
f
g
t i c u l a r ly in the demonstration of the large back effec t on the outer
electron due to the perturbations of the inner orbit which themselves
arise from the presence of the outer electron N evertheless it can
scarcely be regarded as a satisfactory explanation of the h el ium
spectrum Apart from the serious obj ections which may be raised
against his calculation of the perturbations difculties arise if we
try to apply the correspondence principle to L and e s results in
order t o account for the occurrence of two distinct spectra Showing
,

ON T HE SE R I ES S PE CTRA OF T HE E L EME N T S

57

no mutual combinations To explain this fact it see m s necessary

to base the discussion on a more thorough investigation of the
mutual perturbations of the outer and the inner orbits A s a
result of these perturbations both electrons move in such an
extremely complicated way that the stationary states can not be
xed by the methods developed for conditional ly periodic systems
Dr Kramers and I have in the last few years been engaged in such
an investigation and in an address on atomic problems at th e
meeting of the D utch C ongress of N atural and Medical S ciences
held in L eiden A pril 19 19 I gave a Short co m munication of ou r
results For vari ous reasons we have u p t o the present time been
prevented from publishing but in the very near future we hope t o
give an account of these results and of the light which they seem
to throw upon the helium spectrum
The problem presented by the spectra of elements of higher
atomic number is simpler Since the inner system is better dened
in its normal state O n the other hand the difculty of the mec ha n i
cal problem of course increases with the number of the particles in
the atom We O btain an e x ample of this in the case of lithium
with three electro n s The di fferences between the spectral terms
of the lithium spectrum and the corresponding spectral terms of
hydrogen are very small for the variable term O f the principal series
l
o
2
f
u
and
for
the
di
f
se
series
the
other
hand
it
is
very
l
o
o
n
(
(
)
con siderable for the variable term of the sharp series ( 16 :
This
is very di fferent fro m w hat would be expected if it were possible to
descri b e the effect of the inner electron b y a central force varying
in a Simple manner with the distance This must be because th e
parameter of the orbit of the outer electron in the stationary states
corresponding t o the terms of the sharp series is not much greater
than the linear dimensions of the orbits of the inner electrons
A ccording to the principle of correspondence the fr e qu e ncy of rotation
of the m aj or axis of the orbit of the outer electron is to be regarded
as a measure of the deviation of the spectral terms from the corre
s ondi n
hydrogen
terms
In
order
to
calculate
this
frequency
it
p
g
appears necessary to consider in detail the mutual e ffect of all three
electrons at all events for that part of the orbit where the outer
elec t ron is very close to the other t w o electrons E ven if we assumed
that we were fully acquainted with the normal state of the inner
.

ON THE SE RI ES S P E C TRA OF T HE E L EME N T S

58

system in the absence of the outer electron which would b e

e x pected to be similar to the normal state of the neutral helium
atom the exact calculation of this mechanical problem would
evidently form an exceedingly diffi cult task
.

t r u c t u r e o f s er i e s l i n e s F or the spectra of elements

o f still higher atomic number the mechanical problem which has to
be solved in order to describe the motion in the stationary states
becomes still more di fcult This is indicated by the extraordinarily
complicated structure of many of the observed Spectra The fact that
th e series spectra o f the alkali metals which possess the simplest
structure consis t of double lines whose separation increases with
the a tomic number indicates that here we have to do with systems
in which the motion of the outer electron possesses in general a
somewhat more complicated character than that of a simple central
motion This gives rise to a more complicated ensemble of stationary
states It would however appear that in the sodium atom the m aj or
axis and the parameter of the stationary states corresponding to
each pair of spectral terms are given approximately by form ulae
1
7
and
This
is
indicated
not
only
by
the
Similar
part
played
( )
by the two states in the experiments on the resonance radiation of
sodium vapo u r but is also shown in a very instructive manner by
the peculiar e ffect of magnetic elds on the doublets F or small
elds e a ch component splits u p into a large number of Sharp lines
instead of into the normal L orentz t r iplet With increasing eld
strength P aschen and Back found th a t this a nom a lous Z eem a n eect
changed into the normal L orentz triplet of a Single line by a gradual
fusion of the components
This effect of a magnetic eld upon the doublets of the alkali
Spectrum is of interes t in showing the intimate relation of the com
on e n t s and conrms the reality of the Simple explanation of t h e
p
general structure of the spectra of the alkali metals If we m a y
again here rely upon the correspondence principle we have unam
b i gu ou s evidence that the e ffect of a magnetic eld on the motio n
o f the electrons Simply consists in the superposition o f a unifor m
rotation with a frequency given by equation ( 24 ) as in the case 0
the hydrogen atom F or if this were the case the corresponde mo
principle would indicate under all conditions a normal Zeeman e ffe c
C om p l e x

THE SE R I ES S PE C TRA OF THE E L EME N T S

ON
for

59

each component of the doublets I want to emphasize that the

di fference between the Simple e ffect of a magnetic eld which th e
theory predicts for the ne structure of components of the hydrogen
lines and the observed e ffect on the alkali doublets is in no way to
be considered as a contradiction The ne structure components
are n ot analogous to the individual doublet components but each
single ne structure component corresponds to the ensemble of
components ( doublet triplet) which makes up one of the series lines
i n Ry db erg s scheme The occurrence in stron g elds of the e ffect
observed by P aschen and Back must therefore be regarded as a
strong support for the theoretical predicti on of the effect of a mag
netic eld on the ne structure components of the hydrogen lines

It does not appear necessary to assume the anomalous e ffect

o f small elds on the doublet components to be due to a failure of
the ordinary electrodynamical laws for the description of the motion
of the outer electron but rather to be connected with an e ffect of
the magnetic eld on that intimate interaction between the motion
of the inner and outer electrons which is responsible for the occur
rence of the doublets S u ch a view is probably not very di fferent

from the coupling theory by which Voigt was able to account

formally for the details of the anomalous Zeeman effect We might
even expect it to be possible to construct a theory of these e ffects
which would exhibit a formal analogy with the Voigt theory similar
to that between the quantum theory of the normal Zeeman e ffect and
the theory originally developed by L orentz Time u nfortunately
d oes not permit me to enter further into this interesting problem s o
I must refer you to the continuation of my paper in the Transac tions
of the C openhagen A c a demy which w ill contai n a general discussion
of the origin of series spectra and of the e ffects of electric and
magnetic el ds
.

IV

C ON C L US I O N

In this lecture I have purposely n ot considered the question of

the str u cture of atoms and molecules al t hough this is of course mos t
in timately connected with the kind of spectral theory I have de
v e l o e d We are encouraged to u s e results obtained from the spectra
p
since even the simple theory of the hydrogen spectrum gives a
v alue for the maj or axis of the orbit of the electron in the normal
.

ON T HE SE R I ES S P E C T RA OF T HE E LEME NT S

60

state (n 1) of the same order of magnitude as that derived fro m

the kinetic theory of gases In my rst paper on the subj ect I
attempted to Sketch a theory of the structure of atoms and of
molecules of chemical compounds This theory was based on a
simple gen eralization of the results for the stationary states of the
hy d rogen atom In several respects th e theory was supported by
experiment especially in the general way in which the properties
o f the elements change with increasing atomic number Shown most
clearly by Moseley s results I Should like however to u s e this
occasion to state that in view of the recent development of the
quantum theory many of the special assumptions will certainly have
to be changed in detail This has become clear from various sides
by the lack of agreement of the theory with experiment I t appears
no longer possible to j ustify the assumption that in the normal
stat e s the electrons move in orbits of special geometrical Simplicity

like e l ectronic rings C onsiderations relating to the stability of

atoms and molecules against external i nuences and concerning the
possibility of the form ation of an atom by successive addition of
the individual electrons compel us to claim rst that the con
gu r a t i on s of electrons are not only in mechanical equilibrium
but also possess a certain stability in the sense required by
ordinary mechanics and secondly that the congurations employed
m ust be of such a nature that transitions to these from other
stationary states of the atom are possible These requirements are
not in general fu llled by such Simple congurations as electronic
ri ngs and they force us to look a b out for possibilities of more com
plicated motions I t will not b e possible here to consider further
th e se still open questions and I must content myself by referring
to the discussion in my forthcoming paper In closing however
I should like to emphasize once more that in this lecture I have
only intended to b ring ou t certain general points of vie w lying at
the basis of the spectral theory In particular it was my inte ntion
to Show that in spite of the fundamental di fferences between these
po i nts of View and the ordinary conceptions of the phenomena of
radiation i t still appears possible on the basis of the general corre
s on d e n c e between the spectrum and the motion in the ato m to
p
employ these conceptions in a certain sense as guides in the investi
a t i on o f the spectra
g
.

ES S AY 111

THE

O F TH E

S TR UCTU R E

T H E PHY S I CA L
O F T H E ELE ME N T S

ATO M AN D

AN D C H E MI CA L PR O PE R TI ES
1

P RE L I M I N A RY

In an address which I delivered to you about a year ago 1

d escribed the main features of a theory of atomic structure which
I shall attempt to develop this evening In th e meantime this
theory has assumed more denite form and in t w o recent letters
to N a tu r e I have given a somewhat further sketch of the de
v e lo m e n t l
ou are
The
results
which
I
am
about
to
present
to
y
p
o f no nal character ; but I hope to be able to Show you h ow this
view renders a correlation of the various properties of the elements
in such a way that we avoid the di fculties which previously
appeared to stand in the way o f a simple and consistent explanation
Before proceeding however I must ask your forbearance if initially
I deal with matters already known to y ou but in order to intro
duce you to the subj ect it will rst be necessary to give a brief
description of the most important results which have been obtained
in recent years in connection with the work on atomic structure
.

n u c l e a r a t om The conception of atomic structure which

will form the b a s I S of all the following remarks is the s o called
n uclear atom according to which an atom is assumed to consist o f
a nucleus surrounded by a number of electrons whose d i stances
from one another and from the nucleus are very large compared
to the dimensions of the particles themselves The nucleus
possesses almost the entire mass of the atom and has a positive
charge of such a magnitude that the number of electrons in a
n eu t ral atom is equal to the number of the element in the periodic
system the s o called a tomi c n u mber This idea of the ato m which
is due principally to Rutherford s fu ndamental researches on radio
active substances exhibits extremely simple features but j ust this
Simplicity appears at rst sight to present di i c u lt i es in explaining
the proper ties of the elements When we treat this question on
* A dd
re s s d e li e e d b ef r e a j o i nt m e e t i ng of t h e P h y s i c a l a nd C h e m i ca l
S oc i eti s i n C op e nh a ge n O c t ob e r 18 19 21
t N a tu e M a r c h 24 a nd O ct ob er 13 19 21
Th e

'

r ,

T HE STRUC TURE OF T HE A T O M AND

62

TH E

the b asis O f the ordinary mechanical and electrodynamical theories

it is impossible to nd a starting point for an explanatio n of the
marked properties exhibited by the various elements indeed not
ev e n of their permanency O n the one hand the particles of th e
atom apparently could not be a t rest in a state of stable equilibrium
and on the other hand we should hav e to expect that every motion
which might be presen t would give rise to the e mission of el e ctro
magnetic radiation which would n ot cease u ntil all the energy of
the system had been emitted and all the electrons had fallen i n to
the nucleus A method of escapi ng from these di i c u lti es has now
been fo und in the application of ideas belonging t o the q u an t u m
theory the basis of which was l a id by P lanck in his celebrated
work on the law of temperature radiation This represented a
radical departure from previous conceptions Sinc e it was the rst
instance in which the assumption O f a disconti n uity was e mployed
in the formulation of the general laws of nat u re
,

Th e p os t u l a t e s

t h e q u a n t u m t h e or y

The q u antum theory

in the form in which it has been applie d t o the pro b lems of atomic
struct u re rests upon two postulates which have a direct b earin g
on the di fculties mentioned above
A ccording to the rst postu
late there are certain states in which the atom can exist witho u t
emitting radiation although the particles are supposed to have an
accelerated motion relative to one another These s ta ti ona r y s ta tes
a r e in addition supposed t o possess a peculiar kind o f stab ility s o
that it is impossible either to add energy to or remove energy from
the atom except by a process involving a transition of the atom
into another of these states A ccording t o the second postulate
each emission of radiation from the atom resul ting from such a
transition always consists of a train O f purely harmonic waves
The frequency of the s e waves does not depend directly u pon the
motion of the atom but is determined by a fr eq uency r el a ti on
according t o w hich the frequency multiplied by the universal con
stant introduced by P lanck is equal to the total energy emitted
during the process For a transition between t wo stationary states
for which the values of the energy of the atom before and a fter the

emissio n of radiation are E and E respectively we have therefore

of

PHYS I CA L AND CH EM I CA L PROP E RTI ES OF THE E L EME N T S

63

where h is P lanck s cons t a nt and v is th e frequency of the emitted

radiation Time does not permi t me to give a systematic survey
of the quantum theory the recent development of wh i ch has gone
hand in hand with its applications t o atomic structure I shall
ther e fore immediately proceed t o the considera tion of those a p p li
cations of the theory which are of direct importa n ce in con n ectio n
with ou r subj ect

H y d r oge n

We shall commence b y considering the

simplest atom conceivable namely an atom consisting of a nucleus
and one electron If the charge on th e nucleus corresponds to that
o f a single electron and the system consequently is neutral we have
a hydrogen atom Those developments of the quantum theory which
have made possible its application to atomic structure started with
the interpretation of the well known simple spectrum emitted by
hydrogen This spectrum consists of a series of lines the frequencies
of which are given by the extremely simple Balmer form u la
a to

2
( )

where n and n are integers A ccording to the quant u m theory

we Shall now assume that the atom possesses a series of stationary
states characterized by a series of integers and it can be seen how
the frequencies given by formula ( 2) may be derived from the
frequency relation if it is assumed that a hydrogen line is con
n e c t e d with a radiation emitted during a transition between t wo

and if the
of these states corresponding t o the numbers n and n
energy in the nth state apa rt from an arb itrary additive constant
is supposed to be given by the formula

s
( )

The negative Sign is used because the energy of the atom is

measured most simply by the work re quired t o remove the electron
to innite distance from the n ucleus and we shall assume that the
numerical value of the expression on the right hand side of formula
3
is
j
ust
equal
to
this
work
( )
A s regards the closer description of the stationary states we nd
that the electron will very nearly describe an ellipse with the
nucleus i n the foc u s The maj or axis of this ellipse is con nected
,

T HE S T RUC T UR E OF T HE A T O M AND T HE

64

with the energy of the atom in a si mple way and corresponding to

the energy values of the stationary states given by formula (3 )
there are a series of values for the maj or axis 2a of the orbit of the
electron given by the for mula
,

n 6

2a ,,

2
,

where e is the numerical value of the charge of the electron and

the nucleus
O n the whole we may s a y that the spec tr u m of hydrogen shows
us th e for ma ti on of the hy dr ogen a tom since the stationary states
may be regarded as different stages of a process by which the elec
tron under the emission of radiation is bound in orbits of smaller
and smaller dimensions corresponding t o states with decreasing
values of n I t will be seen that this view has certain Charac
t e r i s ti c features in common with the binding process of an electron
to the nucleus if this were to take place according to the ordinary
electrodyn amics but that ou r View di ffers from it in j ust such a
w a y that i t is possible to account for the O bserved properties o f
hydrogen In particular it is seen that the nal result of the
binding process leads t o a quite denite stationary state of the
atom namely that state for which n = 1 This state which corre
s on d s to the minimum energy of the atom will be called the
p
n or ma l s ta te o f the atom I t may be stated here that th e values of
the energy of the atom and the maj or axis of the orbit of the
electron which are found if we put n 1 in formulae ( 3 ) and (4 )
are of the same order of magnitude as the values of the rmness
o f binding of electrons and o f the dimensions of the atoms which
have been obtained from experiments on the electrical and me
c h a n i ca l properties of gases
A more accurate check of formulae
4
and
can
however
not
be
obtained
from
such
a
comparison
3
)
( )
(
because in such experiments hydrogen is not present in the form
o f si mple atoms but as molec u les
The formal basis of the quantum theory consists not only of the
frequency relation but also of conditions which permit the deter
mination of the stationary states of atomic systems The latter
cond i tions like that assumed for the frequency may be regarded as
n atural generalizations of that assump tion regarding the interaction
betwe e n simple e lec t rodynamic systems and a surro u nding eld of
.

P HY SIC AL A N D C H EM IC AL PR O P E RTI E S

OF

TH E

E L E ME N T S

65

electromagnetic radiation which forms the basis of P lanck s theory

1 shall not here go further into the
o f temperature radiation
nature of these conditions but only mention that by their means
th e stationary states are characterized by a number of integers
the s o called qu a ntu m nu m ber s F or a purely periodic motion like
that assumed in the case of the hydrogen atom only a single
quantum number is necessary for the determination of the stationary
states Th i s number determines the energy of the atom and also
the maj or axis of the orbit of the electron but not its excentricity
The energy in the various stationary states if the small inuence
o f the motion of the nucleus is neglected is given b y the follo win g
formula :
.

N
2

2 4

6 777

where e and m are respectively the charge and the mass of the
electron and where for the sake of subsequent applications th e
charge on the nucleus ha s been designated by N e
For the ato m of hydrogen N = 1 and a comparison with
equation ( 3 ) leads t o the following theoretical expression for K in
formula
namely
,

27 1

6 722

This agrees with the empirical value of the constant for the spectrum
of h y drogen within the limit of accuracy with which the various
quantities can be determined
.

H y d r o ge n

e c tr u m a n d X r a y s p e c t r a If in the above
formula we put N 2 which corresponds to an atom consisting of
an electron revolving around a n ucleus with a double charge we
get values for the energies in the stationary states which are four
times larger than the energies in the corresponding states o f the
hydrogen atom and we obtain the following formula for the
spectrum which wo u ld be emitted b y such an atom :
sp

= 4K

<W)

7
( )

This formula represents certain lines which have been known for
some time and which had been attributed to hydrogen on account
of the great simi l arity b etween formulae
and
since
it
had
2
7
( )
( )
B

T HE S T RUC TUR E OF T HE A T O M AND T HE

66

never bee n anticipated that two di fferent substances could exhibit

properties s o closely resembling each other A ccording to the theory
we may ho wever expect that the emission of the spectrum given by
r s t s ta e o the for m a ti on 0
h
h
corresponds
to
the
t
e
e
li
u
m
a
m
o
t
7
g f
f

( )
i e to the binding of a rst electron by the doubly charged nucleus
This interpretation has been found to agree with
of this atom
more recent information For instance it has been possible to
Ob tain this spectrum from pure helium I have dwelt on this point
in order to Show how this in t imate connection b etween the proper
ti e s of tw o elemen ts which at rst sight might appear quite
s u rpris i ng is to be regarded as an immediate expression of the
ch a racteristic simple structure of the nuclear atom A short time
after the elucidation of this question new evidence of extraordinary
interest was obtained o f such a similarity between the properties of
the elem e nts I refer t o Moseley s fundamental researches on the
X ray spectra of the elements Moseley found that these spectra
varied in an extremely Simple manner from one element to the
next in the periodic system It is well known that the lines of
the X ray spectra may be divided into groups corresponding to the
different characteristic absorption regions for X rays discovered by
Barkla AS regard s the K group which contains the most pene
tr a ti ng X rays Moseley found that the strongest line for all ele
ments investigated could be represented by a formula which with
a small simplica t ion can be w ritten
.

N K
2

K is the same constant as in the hydrogen spectrum and N the

atomic number The great signicance of this discovery lies in
the fact that it would seem rmly to establish the View that this
a tomic number is equal to the number of electrons in the atom
This assumption had already been used as a basis for work on
atomic structure and was rst stated by v a n den Broek While
the signican ce of this aspect of Moseley s discovery was at once
clear to all it h as on the other hand been more di fcult to under
stand the very great similarity between the spectrum of hydrogen
and the X ray spectra This similarity is shown not onl y by the
li nes of the K group but also by groups of less penetrating X rays
,

P H Y S I C A L A N D C H EM IC A L

PRO PE RTI E S

O F TH E

E LE MENT S

Thus Moseley found for all the elements b e inv e stigated that the
frequencies of the strongest line in the L group may b e represented
by a formula which with a simplication Similar to that employed
in formula ( 8 ) ca n b e written
v

=N

9
( )

H ere again w e O btain an expression for th e freq u ency which corre

s on d s t o a line in the spectrum which would be emitted by t h e
p
bi ndi ng of a n electr on to a nu cleus whos e cha r ge i s N e
.

t r u c t u r e o f th e h y d r oge n l i n e s This similarity b e

tween the structure of the X ray spectra and the hydrogen spectru m
was still further extended in a very inter e sting manner by S ommer
feld s important theory of the ne structure of the hydrogen lines
The calculation given ab ove of the energy in the stationary states
of the hydrogen system where each state is charac terized by a
single quant u m number rests upon the assumption that the orbit
o f the electron in the atom is simply periodic
This is however
only approximately true It is found that if the change in the mass
of th e electron due to its velocity is taken into consideration the
orbit of the electron no longer remains a simple ellipse b u t i ts
motion may be described as a centr a l moti on O btained by superposing
a slow and uniform rotation upon a simple periodic motion in a
very nearly elliptical orbit For a central motion of this kind the
stationary states are characterized by tw o qu a ntum number s In the
case under consideration on e of these may be so chosen that to a
very close approximation it will determine the energy of the ato m
in the same manner as the q u antum number previously used
determined the energy in the case of a simple elliptical orbit This
quantum number which will always be denoted by n will therefore

be called the principal quantu m number Besides this condition

which to a very close approximation determines the maj or a x is in the
rotating and almost elliptical orbit a s econd condition wi ll b e i mp os e d
upon the stationary states of a central orbit namely that the angular
momentum of the electron about the centre Shall be equal to a whole
multiple of P lanck s constant divided by 27 2 The whole number which
occurs as a factor in this expression may be regarded as t he second
q u antum number and will be denoted by k The latter condi tion xes
5 2
Th e n e

'

T HE ST RUC T UR E

68

T HE A T O M AND T HE

or

t he

e xcentricity of the rotating orbit which in the case of a simple

periodic orbit was u ndetermined It Should be mentioned that the
os s i b l e i m or t a n c e o f the angular momentum in the quantum theory
p
p
was pointed ou t by N i cholson before the application of this theory t o
the spectrum of hydrogen and that a determination of the stationary
states for the hydrogen atom Similar to that employed by S ommer
feld was proposed almost simultaneously by Wilson although the
latter did not succeed in giving a physical application to his results
The simplest description of the form of the rotating nearly
elliptical electronic orbit in the hydrogen atom is obtained by
considering the chord which passes through the focus and is

perpendicular to the maj or axis the s o called parameter The

length 2p of this parameter is given to a very close approximation
by an expression of exactly the same form as the expression for the
maj or axis except that It takes the place of n Using the same
notation as before we have therefore
.

2
2
=
2p
k

27 r N 6 m
2

1
0
( )

For

each of the stationary states which had previously been denoted

by a given value of n we obtain therefore a s e t of statio nary states
corresponding to values of k from 1 to n Instead of the simple
formula ( 5 ) S ommerfeld found a more complicated expression for
the energy in the stationary states which depends on k as well as
Taking the variation of the mass of the electron with velocity
n
into account and neglecting terms O f higher order of magn i tude he
obtained
,

27 7 N
2

47

where c is the velocity of light

C orr esponding to each of the energy values for the stationary
states of the hydrogen atom given by the simple formula ( 5 ) we
obtain n values differi ng only very little fr om on e another since

the second term within the bracket is very small With the aid of
the general frequency relation ( 1) we therefore obtain a number of
components with nearly C oincident frequencies instead of each
hydrogen line given by the simple formula
S ommerfeld has
now shown that this calculation actually agrees with measurements
.

P HY SIC AL A N D C H EM I CAL PR OP E RT I E S

OF

TH E

E LEME N T S

69

of the ne structure This agreement applies not only to the ne

structure of the hydrogen lines which is very di fcult to measure
on account of the extreme proximity o f the components but it is
also possible to account in detail for the ne structure of the helium
lines given by formula ( 7 which has been very carefu lly i n
v e s ti a te d by P aschen
S
ommerfeld
in
connection
with
this
theory
g
also pointed out that formula ( 11) could be applied to the X ray
Spectra Thus he showed that in the K a nd L groups pairs of lines
appeared the di fferences of whose frequencies could be determined
by th e expre s s ion ( 11) for the energy in the stationary states which
correspond to the binding of a Single e l ectron by a nucleus of
charge N e
.

t a b l e In spite of the great formal similarity between

the X ray Spectra and the hyd rogen spectrum i ndicated by these
results a far reaching di fference must be assumed to exist between
the processes which give rise to the appearance of these two types
While the emission of the hydrogen spectrum like the
of spectra
emission of the ordinary optical spectra of other elements may be
assumed to be connected with the binding of an electron by an
atom observations on the appearance and ab sorption of X ray
spectra clearly indicate that these spectra are connected with a
process which may be described as a r eor ga ni z a ti on of the electr oni c
a r r a ng em en t after a disturbance within the atom due to the e ffect
o f external agencies
We should therefore expect that the appear
ance of the X ray spectra would depend not only upon the direct
interaction between a Single electron and the nucleus but also on
the manner in which the electrons are arranged in the completely
formed atom
The peculiar manner in which the properties of the elements
vary with the atomic number as expressed in the periodic system
provides a guide of great value in co nsidering this latter problem
A Simple survey of this system is given in g 1 The number pre
ceding each element indicates the atomic number and the elements

within the various vertical columns form the di fferent periods of

the system The lines which connect pairs of elements in successiv e
columns indicate homologous properties of such elements Com
pared with usual repres e ntations of the periodic system this method
Per i o d i c

T HE S T RUC T UR E OF THE AT OM AND THE

70

proposed more than twenty years ago by Julius Thomsen of indi

cating the periodic variations in the properties of the elements is
more suited for comparison with theories of atomic constitution
The meaning of the frames round certain sequences of elements
within the later periods of the table will be explained later They
refer to certain characteristic features of the theory of atomic
constitution
,

33 S r

I H<1

3 2;

6 c

I ! M:

I!3

WY
30

I6 3

29 0 14

re C d

17 c;

50 3
-

5/5 6

5 2 7&

833 i

F ig

In

an explanation of the periodic system it is natural to as

sume a division of the electrons in the atom into distinct gro u ps
in such a m anner that the grouping of the elements in the system
is attributed to the gr ad u al formation of the groups of electrons
in the atoms as the atomic number increases S uch a grouping
.

P HY SIC AL A N D C H EM I C AL PR O PE RT I E S

OF

TH E

E LEME N TS

71

the electrons in the atom has formed a prominent part of all

more detailed views of atomic structure ever since J J Thom
son s famous attempt to explain the periodic system on the basis
of an investigation of the stability of various electronic c on u r a
g
tions Although Thomson s assumption regard i ng the distribution
of the positive electricity in the atom is n ot consistent with more
recent exp e rimental evidence nevertheless his work has exert e d
great inuence upon the later development of the atomic theory on
accoun t of the many original ideas which it contained
With the aid O f the information concerning the bindin g of
electrons by the nucleus obtained from the theory of the hydrogen
spectrum I attempted in the same paper in which this theory was
s e t forth to sketch in broad outlines a picture of the structure of
the nucleus atom In this it was assumed that each electron in i ts
normal state moved in a manner analogous to the motion i n
the las t stages of the binding of a single electron by a nucle u s
A S in Thomson s theory it was assumed that the electrons moved
in circular orbits and that the electrons in each separate group
during this motion occupied positions with refere nce t o on e another
corresponding to the vertices of plane regular polygons S uch a n
arra ngement is frequently described as a distribution of the electrons

in rings
By m e ans of these assumptions it was possible to
account for the orders of magnitude of the d imensions of the atoms
as well as the rmness with which the electrons were bo u nd by the
atom a measure of which may be obtained by means O f experiments
on the excitation of the various types of spectra
It was not
possible however in this way to arrive at a detailed explanation
o f the characteristic properties of the ele m e n ts even after it had
become apparent from the results of Moseley and the work of
S ommerfeld and others that this Simple picture ought to be ex
tended to include orbits in the fully formed atom characterized by
higher quantum numbers corresponding to previous stages in the
formation of the hydrog e n atom This point has been especially
emphasized by Ve ga r d
The difculty of arriving at a satis factory picture of the atom is
intimately connected with the difculty of accoun ti ng for the p r o

n ou nc e d
stability which the properties of the elements demand
A S I emphasize d when considering the formation of the hydrogen
of

T HE S TRUC TUR E OF T HE AT O M AND T HE

72

atom the postulates of the quantum theory aim directly at this

point but the results obtained in this way for an atom containing
a Single electron do not permit o f a direct elucidation of problem s
like that of the distribution in groups of the electrons in an atom
containing several electrons If we I magine that the electrons in
the groups of the atom are orientated relatively to one another at any
moment like the vertices of regular polygons and rotating in either
circles or ellipses the postulates do not give su fcient information to
determine the di fference in the stability of electronic congurations
w ith di fferent numbers of electrons in the groups
The pec uliar character of stability of the atomic structure de
m a nd e d by the properties of the elements i s brought ou t in an
int eresting way by K ossel in t w o important papers In the rst
paper he Sho w s that a more detailed explanation of the origin of
the high fre quency spectra can be obtained on the basis of the
group str u cture of the atom H e assumes that a line in the X ray
spectrum is due to a process which may be described a s follows :an
electron is removed from the atom by some external action after
which an electron in one of the other groups takes its place ; this
exchange of place may occur in as many ways a s there are groups
This view of the ori gin of the
of more loosely bound electrons
characteristic X rays afforded a simple explanation of the peculiar
absorption pheno m ena observed It has also led to the prediction
o f certain simple relations between the frequencies o f the X
ray
lines from one and the same element and has proved to be a suitable
basis for the classication of th e complete spectrum H owever it has
not b een possible to develop a theory which reconciles in a satis
factory way S ommerfe l d s work on the ne structure of the X ray
lines with K ossel s general scheme As we Shall s e e later the
adoption of a new point of View when considering the stability of
the a tom renders it possible to bring the di fferent results in a natural
way in connection with o ne another
In his second paper Kossel invest i gates the possibilities for an
explanation of the periodic system on the basis of the atomic theory
Without entering further into the problem of the causes of the
division of the electrons into groups or the reasons for the di fferent
stability of the various electronic congurations he points ou t in
conn ection with ideas which ha d already played a part in Thomson s
,

'

P H Y S I C AL

AN D C H EM I C AL PR O P E RT I E S

OF

TH E

E L EME N TS

73

theory how the periodic system affords evidence of a periodic a p

e a r a n c e of especially stable congurations of electrons
These
con
p
gu r a ti on s appear in the neutral atoms of elements occupying the
nal position in each period in g 1 and the stability in question is
assumed in order to explain not only the inactive chemical properties
of these elements but also the characteristic active properties of the
immediately preceding or succeeding elements If we consider for
instance an inactive gas like argon the atomic number of which is 18
we must assume that the 18 electrons in the atom are arranged in
an exceedingly regular conguration possessing a very marked
stability The pronounced electronegati v e C haracter of the preceding
element chlorine may then be explained by supposing the neutral
atom which contains only 17 electrons to possess a tendency to
capture an additional electron This gives rise to a negative chlori ne
i on with a conguration of 18 electrons similar to that occurring
in the neutral argon atom O n the other hand the marked electro
positive character of potassium may be explained by supposing
on e o f the 19 electrons in the neutral atom to be as it were super
u ou s and that this electron therefore i s easily lost ; the rest of the
atom forming a positive ion of potassium having a constitution similar
to that of the argon atom In a corresponding manner it is possible
to account for the electronegative and electropositive character of
elements like sulphur and ca lci u m w hos e atomic nu mbers are 16 and
20 In contrast to chlorine and potassium these elements are divalen t
and the stable conguration of 18 electrons is formed by t he addition
o f t w o electrons to the sulphur atom and by the loss of t w o electrons
fro m the calcium atom D eveloping these ideas Kossel has succeeded
not only in giving interesting e x planations of a large number of
chemical facts but has also been led to certain ge neral conclusions
about the grouping of the electrons in elements belonging to the
rst periods of the periodic system which in certain respects are
in conformity with the results to be discussed in the following
paragraphs K ossel s work was later continued in an interesting
manner by L adenburg with special reference to the grouping of the
electrons in atoms of elements belonging to the later periods of the
periodic table It will be seen that L a de nb u r g s conclusions also
exhibit points of similarity with the results which we shall discuss
later
,

T HE S TRUC T UR E

74
Rec e nt

or

T HE A T O M AND THE

t om i c m o d e l s U p to the pres e nt time it has not been

possible to obtain a satisfactory account based upon a consistent a p
plication of the quantum theory to the nuclear atom of the ultimate
cause of the pronounced stability of certain arrange ments of electrons
N evertheless it has been appare n t for some time that the solution
Should be sought for by investigating the possibilities of a sp a ti a l
d i s tr i bu ti on of the el ectr oni c or bi ts in the atom instead of limiting
the inv estigation to congurations in which all electrons belonging
to a particular group move in the same plane as w a s assumed for
Simplicity in my rst papers on the structure of the atom The
necessity of assuming a spatial distribution o f the congurations
Born
o f electro n s has been drawn attention to by various writers
and L and e in connection with their investigations of the structure
and properties of crystals have pointed ou t that the assumption of
spatial congurations appears necessary for an explanation of these
properties L a nd has pursued this question still further and as

will b e mentioned later has proposed a number of different spatial

atomic models in which the electrons in each separate group of
the atom at each moment form congurations possessing regular
polyhedral sy m metry These models constitute in certain respects
a distinct advance although they have not led to decisive results
on questions of the stability of atomic str u cture
The importance of spatial electronic congurations has in additi on
b e e n pointed ou t by L ewis and L angmuir in connection with their
atomic models Thus L ewis who in severa l respects independently
came t o the same conclusions as Kossel s u ggested that the number
8 ch a racterizing the rst groups of the periodic system might i n
d i c a t e a constitution of the outer atomic groups where the electrons
within each group formed a conguration like the corners of a cube
H e emphasized how a cong u ration of this kind leads to instruc t ive
models of the molecular structure of chemical combinations It is

to be remarked however that such a static model of electronic

conguration will not b e possible if we assume the forces w ithin
th e atom to be due exclusively to the electric charges of the
particles L angmuir who has attempted to develop L ewis con
c e ti ons still further and to account not only for the occurrence of
p
the rst octaves but also for the longer periods of the periodic
system supposes therefore the structure of the atoms to be governed
a

P HY SIC AL A N D C H EM IC AL PR O PE RT I E S

O F TH E

E L EME N TS

75

by forces whose n ature is unk nown to us H e conceives the ato m

t o possess a
cellular structure S O that each electron is in advance
assigned a place in a cell and these cells are arran ged in Shells in
such a manner that the various Shells from the nucleus of the atom
outward contain exactly the same number of places as the periods
in the periodic system proceeding in the direction of increasi n g
atomic number Langmuir s work has attracted much attention
among chemists si nce it has to some extent thrown light on the
conceptions with which empirical chemical science is concerned
O n his theory the explanation of the properties of the various
elements is based on a number of postulates abo u t the structure of
the atoms formulated for that purpose S uch a descriptive theory
i s sharply differentiated from one where an attempt is made to
explain the specic properties Of the elements w i th the aid of
general laws app lying to the interaction between the particles in
each atom The principal task of this lecture will consist in an
attempt to Show that an advance along these lines appears by no
m eans hopeless but on the contrary that with the aid of a con
sistent application of the postulates of the quantum theory it
actu a lly appears possible to obtain an insight into the structure
an d stab ility of the atom
.

11

S ERI ES S P ECT RA AN D T HE C AP T U R E O F EL ECT RON S

B Y AT O M S

W e attack the problem of atomic constitution by asking the

question : H ow may an atom be formed by the successive captur e
a n d binding of the electrons on e by on e in the eld of force s u r
rounding t he nucleus !
Before attempting to answer this question it will rst be
n e cessary to consider in more detail what the quant u m theory
teaches us about the general character of the binding process We
have already seen how the hydrogen spectrum gives u s denite
informa tion about the course of this process of binding the electron
by the nucleus In considering the formation of the atoms of other
elements we have also in their Spectra sources for the elucidation
of the formation processes but the direct information O btained in
this way is not s o complete as in the case of the hydrogen atom
For an element of atomic number N the process o f formation may

T HE S T RUC T UR E OF T HE AT O M AND T HE

76

be regarded as occurring in N stages corresponding with the s u c

c es s i v e binding of N electrons in the eld of the nucleus A Spectrum
must be assumed to correspond to each of these binding processes ;
but only for the rst two elements hydrogen and helium do we
possess a detailed knowledge of these spectra F or other elements
o f higher atomic number where several spectra w i ll be conn ected
with the formation of the atom we a r e at present acquainted with

o n ly two types called the arc and spar

spectra respecti vely
according to the experimental conditions of excitation A lthough
these spectra Show a much more complicated structure than the
hydrogen spectrum given by formula ( 2) and the helium spectrum
given by formula
nevertheless in many c a ses it has b een
possible to nd simple laws for the frequencies exhibiting a close
analogy with the laws expressed by these form u lae
,

If for the sake of simplicity w e dis

regard the complex structure shown by the lines of most spectra
of
o f doublets triplets
f
occurrence
the
freq
u
ency
the
lines
o
(
m any a r e spectra can be represented to a close approximation b y
the Rydberg formula
K
K
Ar e

an d s

p ark

p e c tr a

a lc

where n and n are integral numbers K the same const a nt as i n

the hydrogen spectrum while my and a k are two constants b e
longing to a s e t cha racteristic of the element A Spectru m with a
structure of this kind i s like the hydrogen spectrum called a series
spectrum since the l i nes can be arranged into series in which th e
frequencies converge to denite limiting values These series are
for example represented by formula ( 12) if using two deni te

constants for c a and a k n remains u naltered while 71 a ssumes a

s e ries of success i ve gradually increasing integral values
F ormula ( 12) applies only approximately but it is always found
t h at the frequencies of the spectral lines can be written as in
formulae (2) and
as a difference of two fu nctions of integral
numbers Thus the latter formula applies accurately if the
quantities a ! are n ot considered as constants but as representatives
of a s e t o f series of numbers a !
o
f
characteristic
the
element
n
( )
whose values for increasing n within each seri e s quickly approach

P HYSIC AL AN D C H EM IC A L P R O PE R T I E S

OF

TH E

E L EME N T S

a constant limiting value The fact that the frequencies of the

spectra always appear a s the di fference of two terms the S O called

spectral terms from the combinations of which the complete

spectrum is formed has been pointed out by Ritz who with the
establishment of the combination principle has greatly advanced
the study of the spectra The quantum theory Offers an immediate
interpretation of this prin ciple since according to the frequen cy
relation we are led to consider the lines a s due to transitions
between stationary states of the atom j ust as in the hydrogen
spectrum only in the spectra of the other elements we have to do
not with a Single series of stationary states b u t with a s e t of such
series From formula ( 12) we thus obtain fo r an arc spectrum i f
we temporarily disregard the structure of the individual lines
information abou t an ensemble of stationary states for w hich the
energy of the atom in the nt h state of the kt h series is given by
.

very Similar to the simple formula ( 3 ) for the energy in the station
ary states of the hydrogen atom
A s regards the spark Spectra the structure of which has been
cleared up mainly by F owler s invest i gations it has been possible
in the case of many elements to express t he frequencies a p pr ox i
m ately by means of a formula of exactly the sa m e type as
only with the di fference that K j ust as in the helium spectrum
given by formula
is replaced by a constan t which is four times
as large For the spark spectra therefore the energy v a lues in the
correspondi ng stationary states of the atom will be given by an
expression of the same type as
on ly with the di fference that
K is replaced by 4 K
This remarkable similarity between the structure of these types
o f spectra and the simple spectra given by ( 2) and ( 7 ) is exp lained
simply by assuming the arc spectra to be connected with the l a s t
s ta ge i n the for m a ti on of the neu tr a l a tom consisting in the capture
and binding of the N t h electron O n the other hand the spark
Spectra are connected with the l a s t s ta ge bu t one i n the for ma ti on
1
th
electron
In
these
o the a tom namely the binding of the ( N
)
f
cases the eld of force in which the electron moves will b e much
.

78

S TRUC T UR E OF T HE AT O M AND T HE

T HE

the same as that surrounding the nucleus of a hydrogen or helium

atom respectively at least in the earlier stages of the bin ding
process w here duri ng the grea ter part of its revolution it moves
at a distance from the nucleus which is large in proportion to the
dimensions O f the orbits of the electrons previously bound From
analogy with formula ( 3 ) giving the stationary states of the
hydrogen atom we Shall therefore assume that the n u merical value
of the expression on the right hand Side of ( 13 ) will be equal to the
work requ i red to remove the last captured e lectron from the atom
the binding of which gives ris e to the arc spectr u m of the element
,

S e r i e s d i a gr a m

While the origin of the arc and spark spectra

w a s to this extent immediately i nterpreted on the basis o f the
original simple theory of the hydrogen s p ectr u m i t was S o mmerfeld s
theory of the ne structure of the hydrogen lines which rst gave
us a clear i n sight into th e characteristic di fference between the
hydrogen spectru m and the spark spectrum of helium on the on e
hand and the arc and Spark spectra of other elements on the other
When we consider the binding not of the rst b ut of the subsequent
electrons in the ato m the orbit of the electron u nder consideratio n

a t any rate in the latter stages of the binding process where the
electron last bound comes into intimate interaction with those

previously bound will no longer be to a near approximation a

closed ellipse but on the contrary will to a rst approximation be a
central orbit of the same type as in the hydrogen atom when we
take into account the change with velocity in the mass of the
electron This motion as we have seen may be resolved into a
plane periodic motion upon which a u n iform rotation is superpos ed
in the plane of the orbit ; only the superposed rotation will in this
case be comparatively much more rapid and the deviation of the
periodic orbit from an ellipse much greater than in the case of the
hydrogen ato m F or an orbit of this type the stationary states j ust
as in the theory of the ne structure will be determined by t wo
quantum numbers which we Shall denote by n and 19 connected in
a very Si mple manner with the kinematic properties of the orbit
For brevity I shall only mention that while the quantum number
lo is connected with t h e value of the constant angular momentum
O f the electron about the centre in the simple manner previously
.

AN D C H EM IC AL PR O P E R T I E S

P HY SIC AL

O F TH E

E L E MEN T S

79

indicated the determination of the pri ncipal quantu m number n

requires an investigation of the whole course of the orbit and for
an arbitrary central orbit will not be related in a simple w a y t o
the dimensions of the rotating periodic or b it if this deviates essen
t i a lly from a K eplerian ellipse
,

Q
u

< k= n

( k= 2)

( lr 4)
=

(k=5)

F ig

5
:

5
.

These results are represented in g 2 which i s a repro

duction of an illustration I have u sed on a previous occasion
E
ssay
1
p
and
which
gives
a
survey
of
the
origin
s
e
1
e
(
The black dots represent the s t a
of the sodium spectrum
t i on a r y states corresponding to the various series of spectral terms
Shown on the right by the letters S P D and B These letters
corre spond to the usual notations employed in Spectroscopic
literature and indicate the nature of the series ( Sharp series
principal series di ffuse series etc ) obtained by combinations O f
the corresponding sp e ctral ter ms The distances of the separate
points from the vertical line at the right of the gure are pro
portional to the numerical value of the energy of the atom given
by equation
The oblique black arrows indicate nally the
transitions between the stationary states giving rise to the
appearance of the lines in the commonly O bserved sodium
spectrum The values of n and k attached to the various states
indicate the quantum numbers w hi Oh according to S ommerfeld s
theory from a preliminary consideration might be regarded as
characterizing the orbit of the outer electron F or the sake of
convenience the states which were regarded as corresponding to
the same value of n are connected by means of dotted lines and these
are s o drawn that their vertical asymptotes correspond to the
.

T HE S TRUC TUR E OF T HE A T O M AND T HE

80

terms in the hydrogen spectrum which belong to the same val ue

The course of the curves illus
of the principal quantum number
trates how the deviation from the hydrogen terms may be expected
t o decrease w ith increasing values of k corresponding t o states
where the minimum distance between the electron in its revolution
and the nucleus constantly increases
It Should be noted that even though the theory represents the
principal features of the structure of the series spectra it has n ot
yet been possible to give a detailed account of the spectrum of any
element by a closer investigation of the electronic orbits which may
occur in a Simple eld of force possessing central symmetry A s
I have mentioned already the lines of most spectra Show a complex
structure I n the sodium spectrum for in stance the lines of the
principal series are doublets in dicating that to each P term n ot
on e stationary state but two s u ch states correspond with slightly
different values of the energy This di fference is s o little that
it would not be recognizable in a diagram on the same scale as
g 2 The appearance of these doublets is und oubte d ly due to
the small deviations from central symmetry of the eld o f force
originating from the inner system in consequence of which the
general type of motion of the external electron will possess a
more complicated character than that of a Simple central motion
As a result the stationary states m ust be characterized by more
than two quantum numbers in the sam e way that the occurrence
o f deviations of the orbit of the electron in the hydrogen atom from
a Simple periodic orbit requires that the stationary states of t his
atom shall be Characterized by more than one quantum number
N ow the rules of the quantum theory lead to the introduction o f
a third quantum number through the condition that the resultant
angular momentum of the atom multiplied by 27 is eq ual to a n
entire multiple of P lanck s constant This determines the orienta
tion of the orbit of the outer electron relative to the axis of the
inner system
In this way S ommerfeld Land e and others have shown that it
is possible not only to account in a formal way for the complex
structure of the lines of the series spectra but also to obtain a
promising interpretation of the complicated e ffect of extern al
magnetic elds on this stru cture We shall not enter here on these
.

P HYS I CA L

AND CH EM I CA L P ROP E RTI ES OF THE E L EME N T S

81

problems but shall conne ourselves t o the problem of the xation

uantu
numbers
n and k which to a rst a p pr ox i
o f the t w o
m
q
m ation describe the orbit of the outer electron in the stat i onary
states and whose d etermination is a matter of prime importance
in the followi n g discussion of the formation of the atom l n
the determination of these numbers we at once encounter d i f

as we shall see are intimately

c u l t i e s of a profound nature which
connected with the question Of the remarkable stability of atomic
structure I shall here only remark that the val ues of the quantum
number n given in the gure u ndoubtedly can not be retained
neither for the S nor the P series O n the other hand s o far a s
the values employed for the quantu m nu m ber It are concerned i t
may be stated with certainty that the interpretation of the pro
A
startin
e r t i e s of the orbits which they indicate is corr ect
g
p
point for the investigation of this q u estion has been obtained from
considerations of an entirely di fferent kind from those previo u sly
mentioned which have m ade it possible to establish a close con
n ec t i on between the motion in the atom and the appearance of
spectral lines
,

C o rr e s p o n d e n c e p r i n c i p l e

S o far as the principles of the

quantum theory are concerned the point which has been emphasized
hitherto is the radical departure of these principles from our
usual conceptions of mechanical and electrody namical pheno
mena A s I have attempted t o Show in recent years it appears
possible however to adopt a point of view which suggests that the
quantum theory may nevertheless be regard ed as a rational
generalization of our ordinary conceptions As may be see n fro m
the postulates of the quantu m theory and particularly the frequency
relatio n a direct connection between the spectra and the motion
of the kind required by the classical dynamics is excluded but at
the same time the form of these po stulates leads us to another
relation of a remarkable nature L et us consider an electrodynamic
system and inquire into the nature of the radiation which would
result from the motion of the system on the basis of the ordinary
conceptions We imagine the motion to be decomposed into purely
harmonic oscillations and the radiation is assumed to consist O f
the Simultaneous emission of series of electromagnetic wa ves
.

T HE S TRUC TURE OF T HE AT O M AND

82

TH E

possessing the same frequency as these harmonic components and

intensities which depend upon the amplitudes of the components
A n investigation of the formal basis of the quantum theory shows
us now that it is possi b le to trace the question O f the origin of the
radiation processes which accompany the various transitions back
to an investigation of the various harmonic components which
The possibility that a parti
a ppear in the motion o f the atom
c u la r transition shall occur may be regarded a s being due to the

prese nce of a denitely assignable corresponding co mponent in

the motion This principle of correspondence at the same time
throws light upon a question mentioned several times previously
n amely the relation between the number of quantum numbers
which must be used to d escribe the station ary states of an atom
a nd t h e types to which th e orbits o f the electrons belong
The
classication of these types can be based very simply on a d ec om
position Of the motion into its harmonic components Time does
n ot permit me to consider this question any further and I Shall
conne myself to a statement of some Simple conclusions which
the correspondence principle permits us to draw concerning th e
o ccurrence of transitions be t ween various pairs of stationary states
These conclusions are of decisive importance in the subsequent
arg ument
The Si mplest example of such a conclusion is obtained by
consideri ng an atomic system which contains a particle describing
a p ur ely p er i od i c or bi t and where th e stationary states are charac
t er i z e d by a single quantum number n In this case the motion
can according to F ourier s theorem be decomposed into a simple
series of har monic oscilla tions whose frequency may be written 7 w
where r is a whole number and a) is the frequency of revolution
in the orbit It can now be shown that a transition between two
stationary states for which the values of the quantum number are
respectively equal to n and n will correspond to a harmonic

component for which T = u n This throws at once light upon

the re m arkable difference which exists between the possibilities
of transitions between the stationary states o f a hydrogen atom
on the one hand and of a simple system consisting of an electric
particle capable of executing Simple harmonic oscillations about a
position of equilibrium on the other F or the latter system which
.

'

P HY SIC AL AN D C H EM IC AL PR O PE R T I E S

OF TH E

E L EMEN TS

83

is freq u ently called a P lanck oscillator the energy in the stationary

states is determined by the familiar formula E nhw and with the
aid of the frequency relation we O btain therefore for the radiation
which will be emitted during a transition bet w een two stationary
states v (n n ) to N ow an important assumption which is not
only essential in P lanck s theory of temperature radiation b u t
which also appears necessary to account for the molecular absorption
in the infra red region of radiation states that a harmonic oscillator
w ill only emit and absorb radiation for which the frequency v is
equal to the frequency of oscillation ca of the oscillator We are
therefore compelled to ass u me that in the case of the oscillator
transitions can occur only between stationary states which are
characterized by quantum numbers di ffering by only on e unit
while in the hydrogen Spectrum represented by formula ( 2) all
possible transitions could take place between the stationary states
given by formula
From the point of View of the principle of
correspondence it is seen however that this apparent difculty is
explained by the occurrence in the motion of the hydrogen atom
as opposed to the motion of the oscillator of h a rmonic components
corresponding to values of 7 which are di fferent from 1 ; or u sing
a terminology well known from acoustics there appear overton e s
in the motion of the hydrogen atom
A nother simple example of the application of the correspondence
principle is afforded by a centr a l m oti on to the investigation of
which the explanation of the series spectra in the rst a ppr ox i ma
tion may be reduced Referring once more to the gure of the
sodium spectrum we see that the black arrows which correspond
to the Spectral lines appearing under the usual conditions of
excitation only connect pairs of points in consecutive rows N ow
it is fo u nd that this remarkable limitation of the occurrence of
combinations between spectral terms may quite naturally be
e x plained by an investigation of t he harmonic components into
which a central motion can be resolved I t can readily be Shown
that such a motion can be decomposed into t w o series of harmonic
components whose frequencies can be expressed by To) o and
7 a)
a respectively where 7 is a whole number a) the frequency of
revolution in the rotating periodic orbit and a the frequency o f the
superposed rotation These components correspond with transitions
,

6 2

T HE S T RUC T UR E OF T HE A T O M AND T HE

84

where the principal number n decreases by 7 units while the

quantum number It decreases or increases respectively by on e
unit corresponding exactly with the transitions indicated by the
black arrows in the gure This may be considered as a very
important result becau se we may s a y that the quantum theory
which for the rst time has o ffered a simple interpretation o f th e
fu ndamental principle of combination of spectral lines has at the
same time removed the mystery which has hither t o adhered
to the application of this principl e on account of the apparent
capriciousness of the appearance of predicted comb ina tion lines
E specially attention may be d rawn to the simple interpretation
which the quantum theory o ffers of the appearance observed by
S tark and his collaborators Of certain n ew series of lines which d o
not appear under ordinary circumstances but which are e x cited
when the emitting atoms are subj ect to intense external electric
elds In fact on the correspondence principle this is immediately
explained from an examination of the perturbations in the motion
of the outer electron which give rise to the appearance in t his
motion besides the harmonic components already present in a
Simple central orbit Of a number of constituent harmonic vibra
tions of new type and of amplit udes proportional to the intensity
o f the external forces
It may be of interest to note that an investigation of the
limitation of th e possibility of transitions betwee n stationary
states based upon a simple consideration o f conser vation of angular
mo ment u m during the process of radiation does not contrary to
what has previo u sly been supposed ( compare E ssay I I p
su fce t o thro w light on the remarkably simple structure of series
spectra illustrated by the gure A s mentioned above we must

assume that the complexity of the spectral terms correspondi ng

to given values of n and k which we witness in th e ne
structure of the Spectral lines may be ascribed to states cor
responding to di fferent values of this angular momentum in
which the plane of the electronic orbit is orientated in a di fferent
manner relative to the conguration of the previously bound
electrons in th e atom C onsiderations of conservation of angular
momentum can in connection with the series spectra therefore only
contribute to an understanding of the limitation of the possibilities
,

P HY S I CA L

AND CH EM I CA L P ROP E R TI ES OF THE E L E M E N TS

85

of

combination observed in the peculiar laws applyi n g to the

number of components in the co mplex structure of the lines S o
fa r as the last question is concerned such considerations offer a
direct support for the consequences of the correspondence principle
.

III

FO RMA T I ON O

A T O M S A N D T HE P ERI O D I C T A B LE

A correspon de nce has been Shown t o exist between the motion

of the electron last captured and the occurrence of transitions
b etween the stationary states corresponding to the various stages
of the binding process This fact gives a point of departure for a
choice between the numerous possibilities which present themselves
when considering the formation of t he atoms by the successive
capture and binding of t he electrons A mong the processes which
are conceivable and which according to the quantu m theory might
occur in the atom we shall rej ect those whose occurrence can not be
regarded as consistent with a correspondence of the required nature
.

Fi r s t P e r i o d

H y d r o ge n H e l i u m

It will n ot be necessary t o
concern ourselves long with the question of the constit u tion of the
hydrogen atom F rom what has been said previously we may assume
that the nal result of the process of bi ndi ng of the r s t el ectr on in
any atom will be a stationary state where the energy of the a t om
is given by
if we put n 1 or more precisely by formula
if we put n = 1 and lo 1 The orbit o f the electron will be a circle
whose radius will be given by formulae
if n a n d lo are each
put equal to 1 S uch an orbit will be called a l quantum orbit
and in general an orbit for which the principal quantum number
has a given value n will be called an n quantum orbit Where it
is necessary to di fferentiate between orbits correspo nding to various
values of the q uantum num b er lo a central orbit characterized by
given values of the quantum numbers n and 19 will be referred to
a s an n! orbit
In the question of the constitution of the helium atom we meet
the much more complicated problem O f the bi ndi ng of the s econd
el ectr on
Information a bout this binding process may howe v er be
obtained from the arc spectrum of helium This spectrum as
opposed t o most other simple spectra consists of two complete
systems of li n e s with freq u encies given by formulae of the type
.

T HE S T RUC TUR E OF T HE A T O M AND T HE

86

On

this account helium was at rst assumed to be a mi x ture

or t h oh e li u m
and p a r h e li u m but now we
o f two different gases
know that the two spectra simply mean that the binding of the second
electron can occur in two di fferent ways A theoretical e x planation of
the main features of the helium spectru m has r ec en tly b e e n attempted
in an interesti ng paper by L and e H e supposes the emission of the
or t h oh e li u m Spectru m to be due to transitions between stationary
states where both electrons move in the same plane and revolve
in the same sense The p a r h e l i u m Spectrum on the other hand is
ascribed by him to stationary states where the planes of the orbits
form an angle with each other Dr Kramers and I have made a
closer investigation o f the interaction between the two orbits in
the di fferent stationary states The results of ou r investigation
w hich was be g un several years before the appearance of L and e s
work have n ot yet been published Without going into details
I may say that even though our results in several respects di ffer
materially from those of L and e ( compare E ssay II p
we agree
with his general conclusions concerning the origin of the ortho
helium and p a r h e li u m spectra
The nal result of th e binding of the second electron is inti
m a tely related t o the origin of the two helium spectra Important
in form a tion on this point has been ob ta i ne d t e c en tly by Franck
and his c o workers A s is well known he has thrown ligh t upon
many feat ures of the struct u re of the atom and of the origin
the e ffect of bombarding atoms by
of spectra b y observing
el e ctrons of vario u s velocities A short time ago these experiments
Showed that the impact of electrons could bring helium into a

metastable state from which the atom cannot return to its

normal state by m eans of a Simple transition accompanied by the
emission of radiation but only by m ean s of a process analogous t o
a chemical reaction involving interaction w ith atoms of other
elements This result is closely connected with the fact th a t the
binding of the second electron can occur i n two di fferent ways as
is shown by the occurrence of two distinct spectra Thus i t is
evident from Franck s experiments that the normal state of the
atom is the last stage i n the binding process involving the emission
of the p a r h e l i u m spectrum by which the electron last captured as
well as the one rst capture d will be bound in a 1 orbit The

,l

P HY SIC AL A N D C H EM IC AL P R O PE RT I E S

E L EME N TS

O F TH E

87

metastable state on the contrary is the nal stage of the process

giving the or t hoh e li u m spectrum In this case the second e l ectron
a s opposed to the rst will move in a 2 orbit
This corresponds to
a rmness of bindi n g which is about s i x times less than for the
electron in the normal state of the atom
If we n ow consider somewhat more closely this app a rently
surpri sing result it is found that a clear grasp of it may be obtained
fr om the point of view of correspondence I t can be sho w n that
the coherent class of motions to which the or t hohe li u m or b its
belong does not contain a 1 orbit If on the whole we would claim
the existence of a state where the two electrons move in 1 orbits
in the same plane and if in addition it is claimed that the mo t ion
Should possess the periodic properties n ecessary for the denitio n
o f stationary states then there seems that no possibility is afforded
other than the assumption that the two electrons move around the
nucleus in one and the same orbit i n such a manner that at each
moment they are situated at the ends of a diameter This extremely
simple ring congu r a ti on might be expected to correspond t o
the r m e s t possible binding of the electrons I n the atom and it
was on this account proposed as a model for the helium a tom in
my rst paper on atomic structure If however we inquire abou t
the possibility of a transition from on e of the or th oh e li u m sta t es
to a conguration of th i s type we meet conditions which are very
different from those which apply to transitions between two of
the or thoh e li u m orbits In fact the occurrence of each of these
transitions is due to the existence of well de ne d corresponding
consti tuent harmonic vibration in the central orbits which the outer
electron describes in the class of motions to which the stationary
st ates belong The transition we have to discuss on the oth e r
hand is one by which the last captured electron is transferred from

a state in which it is moving outside the other to a state in which

it moves round the nucleus on equal terms with the other electron
N ow it is impossible to nd a s e r i es of Simple intermediate forms
for the motion of those two electrons in which the orbit of the last
capture d electron exhibits a su fcient Similarity to a central motion
that for this transition there could be a correspondence of the
necessary ki nd It is therefore evident that where the two electron s
move in the same plane the electron captured last can not b e
,

T HE ST RUC T UR E OF T HE A TO M A N D THE

88

bound rmer than in a 2 orbit If on the other hand we consider

the binding process which accompanies the e mission of the p a rh e li u m
spectrum and where the electrons in the stationary states move in
orbi t s w hose planes for m angl es with one another we meet essen
t i a lly di fferent conditions A corresponding intimate change in the
interaction between the electron last captured and the one previously
bound is not required here for the two electrons in the atom to
become equivalent We may t herefore imagine the last stage of
the binding process to take place in a manner Similar to those
stages corresponding to transitions between orbits characterized by
greater values of n and k
In the n or ma l s ta te of the heli u m a tom the two electrons must
be ass u med to move in equivalent 1 orbits As a rst approximation
these may be d escribed as two circular orbits whose planes make
an angle of 120 with one another in agreement with the conditions
which the angular mo m entum of an atom according to the quantum
theory must satisfy O n account of the interaction between the
two electrons these planes at the same time turn slowly around
the xed impulse axis of the atom S tarting from a distinctly
di fferent point of view K emble has recently suggested a similar
model for the helium atom H e has at the same time directed
atten tion to a possible type of motion of very marked symmetry
in which the electrons during their entire revolution assume
symmetrical positions with reference to a xed axis K emble has
not ho w e ver investigated this motion further P revious to the
a ppearance of this paper Kramers had commenced a closer investi
a t i on of precisely this type o f motion in order to nd out to what
g
ex t ent i t was possible from such a calculation to account for the
rmness wit h which the electrons are bound in the helium atom
that is to account for the ionization potential E arly measurements
o f this potential had given values corresponding approximately to
that which would resul t from the ring c ongur a ti on already men
t i on e d
This requires
as much work to remove a single
electron as is necessary t o remove an electron from the hydrogen
atom in its normal state A s the theoretical value for the latter
amount of work which for the sake of Simplicity will b e r ep r e
sented b y W corresponds to an ionization potential of
volts
the ionization potential of helium would be expected to be 28 8
1

PHYSIC AL AN D C H EM IC AL P R OP E RTI E S

E L EME NT S

O F TH E

89

volts Recent and more accurate determinations however have

given a v alue for the ionization potential of helium which is con
o f 25 volts
lo
er
and
lies
in
the
neighbourhood
This
s i de r a b l
w
y
showed therefore the untenability of the ring c ongu r a ti on quite
independently of any other considerations A carefu l investigation of
the spatial atomic conguration requires elaborate calculation and
K ramers has not yet obtained nal res u lts With the approximation
to which they have been s o far completed the calculations point to
the possibi lity of an agreement with the e x perimental results The
nal resu lt may be awaited with great interest since it o ffers in
th e si mplest case i m aginable a test of the principles by which we
are attempting to determine stationary states of atoms containing
more than one electron
Hydrogen and helium a s seen in the survey of the periodic
system given in g 1 together form the rst period in the system
The great
o f elements since helium is the rst of the inacti v e gases
di fference in the chemical properties of hydrogen a nd helium is
closely related t o the great di fference in the nature of the binding
This is directly indicated by the spectra a nd
of the electron
ionization potentials While heliu m possesses the highest known
ionization potential of all the elements the binding of the electron
in the h y drogen atom is su fcien tly loose to account for the tendency
of hydrogen to form positive ions in aqueous solutions and chemical
combinations F urther consideration of this particular ques tion
requires however a comparison between the nature and rmness
of the electronic congurations of oth er atoms and i t can therefore
not be discussed at the moment
,

S e c o n d P e ri od

L i th i um N e o n

When considering the atomic

structure of elements which contain more than two electrons in the
neutral atom we shall assume rs t of all that what has previously
been said about the formation of the helium atom will in the main
features also apply t o the capture and binding of the rst t wo
electrons These electrons may therefore in the normal s tate of
the atom be regarded as moving in equivalent orbits characterized
by the quan tum symbol
We obtain direct information about
the bi ndi ng of the thi r d elec tr on from the spectrum of lithium
This spectrum shows the existence of a n umber of series of
.

T HE S TRUC T URE OF T HE A T O M AND T HE

90

stationary states where the rmness with which the last captured
electron i s bound is very n early the same as in the stationary states
These states correspond to orbits where lo
o f the hydrogen atom
is greater than or equal to 2 and where the last captured electron
moves en t irely outside the region where the rst two electrons
move But in addition this spectrum gives us information about a
series of states correspon ding to lo : 1 in which the energy di ffers
esse n tially from the corresponding stationary states of the hydrogen
atom In these states the last captured electron even if it remains
at a considerable distance from the nucleus during the greater part
o f its revolution
will at certain moments during the revolution
approach to a distance from the nucleus which is of the same order
of magnitude as the dimensions of the orbits o f the previously
bound electrons O n this account the elec t rons will be bound with
a rmness which is considerably greater than that with which the
electrons are bo u nd i n the stat i onary states of the hydrogen atom
corresponding to the same value of n
N ow as regards the lithium spectrum as well as the other alkali
spectra we are s o fortunate (s e e p 3 2) as to possess denite evidence
about the normal state of the atom from experiments on selec tive
absorption In fact these experiments tell us that the rst member

of the sequence of S terms corresponds t o this state

This term
corresponds t o a strength of binding which is only a little more than
a third of that of the hydrogen atom We must therefore conclud e
that the outer electron in the normal state of the lithium atom
moves in a 2 orbit j ust as the outer electron in the me tastable
state of the helium atom The reason why the binding of the
outer electron can not proceed to an orbit characterized by a smal ler
value for the total quantum number may also be considered as
analogous in the two cases In fact a transition by which the third
electron in the lithium atom was ultimately bound in a 1 orbit
would lead to a state in the atom in which the electron would play
an equivalent part wi th the two electrons previously bound S uch
a process would be of a type entirely di fferent from the transitions
between the stationary states connected with the emission of the
lithium Spectrum and would contrary to these not exhibit a
correspondence w ith a harmonic component in the motion of the
atom
,

P HY SIC AL A N D C H EM IC AL PR O P E RT I E S

OF

E L EME N T S

TH E

91

We obtain therefore a picture of the formation and structure of

the lithium atom which o ffers a natural explanation of the great
di fference of the chemical properties of lithium from those of helium
and hydrogen This di fferen ce is at once explained by the fact that
the rmness by which the last captured electron is bound in its
2 orbit in the lithium atom i s only about a third of that with which
the electron in the h y d rogen atom is held and almost v e times
smaller than the rmness of the binding of the electrons in the
helium atom
What has been said here applies not alone to th e formation of
the lithium atom but may also be assu m ed to apply to the binding
o f the third electron in every atom so that in contrast to the rst
two electrons which move in I orbits this may be assumed to move
in a 2 orbit A s regards the bi ndi ng of the four th fth a nd s i x th
e l ectr ons in the atom we do not possess a simi lar guide as no Simple
series spectra are known of beryllium boron and carbon A lthough
conclusions of the same degree of certainty can not be reached it
seems possible however to arrive at results consistent with general
physical and chemical evidence by proceeding by means of c on
siderations of the same kind as those applied to the binding of the
rst three electrons In fact we Shall assume that the fourth fth
and sixth electrons will be bound in 2 orbits The reason why the
binding of a rst electron in an orbit of this type will not prevent the
cap ture of the o t hers in two quanta orbits may be ascribe d to the fact
that 2 orbits are not circular but very excentric F or example the
3 r d electron can n ot keep the remaining electrons away from the inner
system in the same way in which the rst two electrons bound i n
the lithium atom prevent the third from being bound I n a
I quantum orbit Thus we shall expect that the 4 t h 5 t h and 6 th
electrons in a similar way to th e 3 r d will at certain moments of
their revolution enter into the region where the rst t w o
bound electrons move We must not imagine however that these
v isits into the inner syste m take
lace
at
the
same
time
but
p
that the four electrons visit the nucleus sep a rately at equal
intervals of time In earlier work on atomic structure it was sup
posed that the electrons i n the various groups in the atom moved
in separate regions within the atom and that at each moment the
electrons within each separate group were arranged in congurations
,

T HE S T RUC T UR E OF T HE A TO M AND T HE

92

possessing symmetry like that of a regular polygon or polyhedron

A mo n g other thi ngs this involved that the electrons in each group
were supposed to be at the point Of the orbit nearest the nucleus
at the same time A structure of this kind may be described as on e
where the motions of the electrons within the groups are coupled
together in a manner which is largely independent of the interaction
between the various groups O n the contrary the characteristic
feature of a structure like that I have suggested is the i nti ma te
c oup li ng betw een the m oti ons o
h
l
t
n
h
r ou s
t
e
e
r
o
s
i
n
t
v
r
i
u
s
ec
e
a
o
f
g
p
characterized by di fferent quantum numbers as well as the gr ea ter
i n d ep e nd ence i n the m od e of bi n di ng w i thi n one a nd the s a m e gr oup
o
e l ectr ons the orbits of which are characterized b y the same
f
quantum number In emphasizing this last feature I have t wo
points in mind F irstly the smaller e ffect of the presence of pre
v i ou s l
f
bound
elec
rons
on
the
rmness
binding of s u cceeding
t
o
y
electrons in the same group S econ d ly the way in which the motions
o f the electrons within the group reect the indepe n dence both of
the processes by which the group can be formed and by which it
can be reorganized by change of position of the di fferent electrons
in the atom after a disturbance by external forces The last point
will be considered more C losely when we deal with the origin and
n ature of the X ray spec t ra ; for the present we shall continue the
co nsideratio n of the structure of the atom to which we are led by
the i nvestigation of the processes connected with the successive
capture of the electrons
The preceding considerations enable us to understand the fact
that the two elements beryllium and boron immediately succeeding
lithium can appear e le c t r op os i t i v e ly with 2 and 3 valencies r e s p ec
F or like the third
t i v e ly in combination with other substances
electron in the lithiu m atom the last captured electrons in these
elements will be m u ch more lightly bound than the rst two
electrons A t the same time w e understand why the elect ropositive
character of these elements is less marked than in the case of
lithium since the electrons in the 2 quanta orbits will be much
m ore rmly bound on account of the s tronger eld in which they
are moving N e w con d itions arise ho w ever in the case of the
n ext element carbon as this element in its typical chemical com
b i n a t i on s can n ot b e s u pposed to occur as an ion but rather as a
.

PHY S I CA L

AND CH EM I CAL PROP ER T I ES OF THE EL EME N T S

93

neutral atom This must be assumed to be due n ot only to the great

rmness in the binding of the electrons but also to be an essential
consequence of the symmetrical conguration of the electrons
With the binding of the 4t h 5 t h and 6 t h electrons in 2 orbits
the spatial symmetry of the regular conguration of the orbits
must be regarded as steadily increasing unti l with the binding of
the 6 th electron the orbits of the four last bound electrons may be
expected to for m an exceptionally symmetrical conguration in
which the normals to the planes O f the orbits occupy positions
relative to one another nearly the same as the lines from the centre
t o the vertices o f a regular tetrahedron
S uch a conguration
of g r oups o f 2 quanta orbits in the carbon atom seems capable
o f furnishing a suitable foundation for explaining the structure of
organic compounds I shall not discuss this question any further
for it would require a thorough study of the in t eraction between
the motions of the electrons in the atoms forming the molecule
I might mention however that the types of molecular models to
which we are led are very di fferent from the molecular mode ls
w hich were suggested in m y rst papers
In these the chemi cal

valence bonds were represented by electron rings of the same

type as those which were assumed to compose the groups of
electrons within the i ndividual atoms It is nevertheless possible
t o give a general explanation of the chemical properties of the
elemen ts without touching on those matters at all This is largely
due t o the fact that the structures of combinations of atoms of the
same element and of many organic compounds do not have the
same Signicance for ou r purpose as those molecular structures in
which the individual atoms occur a s electrically charged ions The
latter kind of co mpounds to which the greater num b er of si mple

inorganic compounds belong is frequently called heteropolar and

possesses a far more typical character than the rst compounds

which are called homoeopolar and whose properties to quite a

different d egree exhibit the individual peculiarities of the elements
My main purpose w i ll therefore be to consider the tness which
the congurations of the electrons in the various atoms Offer for
the formation of ions
Before leaving the carbon atom I should mention that a model
O f this atom in which the orbits of the four most lightly bound
.

94

T HE

S T RUC TUR E OF T HE AT O M AND T HE

electrons possess a pronounced tetrahedric symmetry had already

been suggested by L and e In order to agree with the measurements
o f the size o f the atoms he also assumed that these electrons moved
in 2 orbits There is however this difference between L and e s
view and that given here that while L and e deduced the character
i s ti c properties of the carbon atom solely from an investigation of
the simplest form of motion which four electrons can e x ecute
employing spatial symmetry our View originates from a considera
tion of the stability o f the whole atom For our assumptions about
the orbits of the electrons are based directly on an investigation of
the interaction between these electrons and the rst two bound
electrons The result is that our model of the carbo n atom has
dynamic properties which are essentially di ffere nt from the proper
ties O f L and e s model
I n orde r t o a c count for the properti e s of the elem ents i n the s econd
ha lf of the s econd p er i od it will rst of all be necessary to Show
why the conguration of ten electrons occurring in the neutral atom
o f neon possesses such a remarkable degree of stability
P reviously
it has been assumed that the properties of this conguration were
due to the interaction between eight electrons which moved in
equivalent orbits outside the nucleus and an inner group of two
electrons like that in the helium atom I t will be seen however
that the solution m ust be sought in an entirely di fferent direction
It c a n not be expected that the 7 th electr on will b e bound in a 2 orbit
equivalent to the orbits of the four preceding electrons The occur
rence of ve such orbits would s o denitely destroy the symme try
in the interac tion of these electrons that it is inconceivable that a
process resulting in the accession of a fth electron to this group
would be in agreement with the correspondence principle O n the
contrary it will be necessary to assume that the four electrons in
their exceptionally symmetrical orbital conguration will keep ou t
later captured electrons with the result that these electrons will be
b ound in orbits of other types
The orbits which come into consideration for the 7 t h electron in
the nitrogen a tom and the 7 th 8 t h 9 th and l 0 th electrons in the
atoms of the immediately following elements will be circular orbits
o f the type 2
The diameters of these orbits are considerably larger
than those of the 1 orbits of the rst two electrons ; on the other
.

2.

P H Y S I C AL

AN D C H EM IC AL P R O P E RTI E S

OF

TH E

L EME N T S

95

hand the outermost part of the excentric 2 orbits will extend some
distance beyond these circular 2 orbits I shall not here discuss the
capture and binding of these electrons This requires a further i n
v es t i a t i on of the interaction between the motions of the electrons
g
in the two types of 2 qua nta orbits I shall Simply mention that
in the ato m of neon in which we will assume that there are four
electrons in 2 orbits the planes of these orbits must be regarded not
only as occupying a position relative to on e another characterized
by a high degree of spatial symmetry but also as possessing a
conguration harmonizing with the four elliptical 2 orbits A n
interaction of this kind in which the orbital planes do not
coincide can be attained only if the congurations in b oth s ub
groups exhibit a systematic deviatio n from tetrahedral symmetry
This will have the result that the electron groups with 2 quanta
orbits in the neon atom will have only a Single axis of symmetry
which must be supposed to coincide with the axis of symmetry of
the innermost group of t w o electrons
Before leaving the description of the elements within the second
period it may be pointed out that the above considerations o ffer a
basis for interpreting that tendency of the neutral atoms of oxygen
a n d uorine for capturing further electrons which is responsible for
the marked electronegative Character of these elements In fact
this tendency may be ascribed to the fact that the orbits of
the last captured elec trons will nd their place within the region
in which the previously captured electrons move in 2 orbits This
suggests an e xplanation of the great difference between the pr o
e r t i es of the elements in the latter half of the second period of the
p
periodic system and those of the elements in the rst half in whose
atoms there is only a single type of 2 quanta orbits
,

Th i r d P er i o d

S o d i u m A r go n

We shall now co nsider the

structure of atoms of elements in the third period of the periodic
system This brings us i m me di a t e ly t o the q u estion of the bi ndi ng
h
1
o
t
e
1
h
l
t
r
n
d
in
the
atom
H
ere
we
meet
con
itions
which
e
ec
o
t
f
in some respects are analogous to those connected with the binding
o f the 7 t h electron
The same type of argument that applied to
the carbon atom shows that the symmetry of the conguration in
the neo n atom would b e essentially if not entirely destroyed by
.

T HE

96

S T RUC T UR E OF T HE A TOM AND T HE

the addition of another electron i n an orb it of the same type as

that in which the last captured electrons were bound Just as in
the case of the 3 r d and 7 t h electrons we ma y therefore expect t o
meet a new type of orbit for the 1 1t h electron in the atom and the
orbits which present themselves this time are the 3 orbits An
electron in such an orbit will for the greater part of the ti m e remain
outside the orbits of the rs t ten electrons But at certain moments
during the revolution it will penetrate n o t only into the re gion of
the 2 quanta orbits but like the 2 orbits it will penetrate t o
distances from the nucleus which are smaller than t he radii of
the I quantum orbi t s of the two electrons rst bound This fact
which has a mos t important bearing on the stability of the atom
leads to a peculiar result as regards the binding of the 11th electron
In the sodium atom this electron will move in a eld which s o far
as the outer part of the orbit is concerned deviates only very little
from that surrounding the nucleus in the hydrogen atom but the
dimensions of this part of the orbit will nevertheless be essentially
di fferent from the dimensions of the corresponding part of a 3
orbit in the hydrogen atom This arises fro m the fact that even
though the e lec tron only enters the inner conguration of the rst
ten electrons for short interval s during its revolution this part of
the orbit will nevertheless exer t a n esse ntial inuence upon the
determin ation of the principal quantum number This is directly
related to the fact that the motion of the electron in the rst part
o f the orbit deviates only a little fro m the mo t ion which each of
the previously bound electrons in 2 orbits executes during a com
revolution
The
uncertainty
which
has
prevailed
in
the
l
e te
p
determination of the quantum numbers for the statio n ary states
corresponding to a spectrum like that O f sodium is co nnected with
this This question has been discussed by several physicists From
a comparison of the spectral terms of the various alkali metals
Ros c hd e s tw e n s ky has drawn the conclusion that the normal state
does not as we might be inclined to expect a priori correspond to
a 1 orbit as shown in g 2 on p 7 9 but that this state corre
c h r Odi n ge r has arrived at a similar result
s on d s to a 2 orbit
S
p
in an attempt t o account for t he great di fference between the
S terms and the terms in th e P and D series o f the alkali spectra

H e assumes that the outer e lectron in the states corresponding

.

PHY S I CA L AND CH EM I CA L PROP E RT I ES OF THE E L EME N T S

97

the
terms
i n contrast t o those corresponding to the P and
to
S
D terms penetrates partly into the region of the orbits o f the
inner electrons during the course of its revolution These investi
a t i ons contain without doubt important hints but in reality the
g
c onditions must be very di fferent for the different alkal i spectra
Instead of a 2 orbit as in lithium we must thus assume for
th e spectrum of sodium not only that the rst spectral term i n
the S series corresponds t o a 3 orbit but also as a more detailed
consideration shows that the rst term in the P series corresponds
not to a 2 orbit as indicated in g 2 but to a 3 orbit If the
n u mbers in t h is gure were correct it would require a mong othe r
things that the P terms should be smaller than t he hydrogen term s
.

Fig

corresponding to the same principal quantum number This would

mean that the average effect of the inner electrons could be described
a s a repulsion greater than would occur if their total electrical charge
were united in the nucleus This however can not be expected from
The fact tha t the last captured electron
o u r v i e w of atomic structure
at any rate for low values of k revolves partly inside the orbi t s of the
previously bound electrons will on the contrary involve that the
presence of these electrons will gi ve rise to a virtual rep ulsion
which is considerably smaller t ha n t ha t which would be due to
their com bined charges Instead of the curves drawn bet ween
points in g 2 which represent stationary states corresponding
t o t h e same value of the principal quantum number running fro m
right t o left we obtain curves w h ich run from left to right as
is in dicated in g 3 The stationary s tates are labelled with
.

98

T HE

S T RUC T URE OF T HE A T O M AND T HE

t
o the structure I have described
u
antu
num
b
ers
corresponding
m
q
A ccording to the view underlying g 2 the sodium spectrum
might be described si mply as a distorted hydrogen spectrum
whereas according to g 3 there is not only distortion but also
complete disappearance of certain terms of low quantum numbers
It may be stated that this Vie w not only appears to O ffer an ex
planation o f the magnitude of the terms but that the comple x ity
o f the terms in the P and D series nds a natural explanation in
the deviation of the conguration of the ten electrons rst bound
from a purely central symmetry This lack of symmetry has its
origin in the conguration of the t w o innermost electrons and

transmits itself to the outer parts of the atomic structure since

t h e 2 orbits penetrate partly into the region of these electrons
This vie w of the sodium spectrum provides at the same time an
immediate explanation of the pronounced electropositive properties
of sodium Since the last bound electron in the sodium atom is still
more loosely bound than the last captured electron in the lithium
atom In this connection it might be mentioned that the increase
in atomic volume with increasing atomic number in the fam ily of
th e alkali metals nds a simple explanation in the successively
looser binding o f the valency electrons In his work on the X ray
spectra S ommerfeld at an earlier period regarded this increase in
the ato mic volumes as supporting the assumption that the principal
quantum number of the orbit of the valency electrons increases by
unity as we pass from one metal to the nex t in the family His
later investigat ions on the series spectra have led him however
d en itely to abando n this assumption A t rst sight it might also
appear to entail a far greater increase in the atomic volume than
that actually observed A Simple e x planation of this fact is h ow
e ver a fforded by realizing that the orbit of the electron will run
partly inside the region of the i nner orbit and tha t therefore the
e ffective quantum number which corresponds to the outer almost
e lliptical loop will be much smaller than the principal quantum
number by w hich the whole central orbit is described It may
be mentioned that Ve ga r d in his investigations on the X ray Spectra
h as also proposed the assump tion of successively increasing quantum
n u mbers for the electronic orbits in the various groups of the atom
reckoned from the n u cleus outward H e has introduced a ssumptions
.

PHY S I CA L A N D CH E M I CA L PRO P E RTI ES

or

T HE E LE M E N TS

99

bout the rel a tions betwee n the numbers of electrons in the various
groups of the atom and the lengths of th e periods in the periodic
system which exhibit certain formal similarities with the resul t s
presented here But Ve ga r d s considerations do not o ffer points of
departure for a further consideration of the evolution and stability
of the groups and consequently no basis for a detailed interpretation
of the properties o f the elements
When we consider the elements following sodium in the third
p eriod of the periodic system we meet in the bi ndi ng of the 12th
13 th a nd 14 th el ectr ons conditions which are analogous to those
we met in the binding of the 4 t h 5 th and 6 t h electrons In the
elements of the third periods however we possess a far more
detailed knowledge of the series spectra Too little is known
about the beryllium spectru m to dra w conclusions about the
bin ding of the fourth electron but we may infer directly from the
well known a r e spectrum of magnesium that the 12th electron
in the atom of this element is bound in a 3 orbit A s regards
the binding of the 13 th electron we meet in aluminium an
absorption spectrum di fferent in structure to that O f the alkali
metals In fact here not the lines of the principal S CI I CS but the
lines of th e sharp and diffuse series are absorption lines C ons e
quently it is the rst member of the P terms a nd not of the S
terms which corresponds to the normal state of the al u minium
a tom and we m ust assume that the 13 th electron is bound in
a 3 orbit This however would hardly seem to be a general
property of the bin ding of the 13 th electron in atoms but rather
to arise from the Special conditions for the binding of t he last
electron in an atom where already there are two other electrons
bound a s loosely as the valency electron O f aluminium A t the
present state O f the theory it seems best to assume that in the
silicon atom the four last captured electrons w
ill move in 3
orb its forming a conguration possessing symmetrical properties
similar to the o u ter conguration of the four electrons i n 2 orbits
in carbon L ike what we assumed for the latter conguration we
shall expect that the conguration of the 3 orbits occurring for the
rst time in Silicon possesses such a completion that the addition
of a further electron in a 3 orbit to the atom o f the following ele
m e n ts is i mpossible a n d that the 15 th electr on in the elements of
a

10 0

S TRUC T UR E OF T HE A T O M AND T HE

THE

higher atomic number will be bound in a new type of orb it In this

case however the orbits wi t h which we meet will not be circular
a s in the capture of the 7 t h electron but will be rotating excentric
orbits of the type
This is very closely related to the fact men
t i on e d above that the non circular orbits will correspond to a
rmer binding than the circular orbits having the same value for
the principal quantum number since the electrons w ill at certain
moments pene trate much farther into the interior of the atom
E ven though a 3 orbit will not penetrate into the inner m ost c on
guration of 1 orbits it will penetrate to distances from the nucleus
which a re considerably less than the radii of the circular 2 or b i ts
In the case of the l 6 th 17 t h and 18 th electrons the conditions are
similar to those for the 15 th S o for argon we may expect a c on
guration in which th e ten innermost electrons move in orbits of
the same type as in the neon atom while the last eight e lectrons will
form a congura tion o f four 3 orbits and four 3 orbits whose
symmetrical properties mu s t be regard ed as closely corr esponding
A t the
t o the con g uration of 2 quanta orbi t s in the neon atom
same time as this picture sugges ts a qualitative explanation of the
similarity of the chemical properties of the elemen t s in the latter
part of the second and third periods it also opens up the possibility
of a natural explanation o f the conspicuous di fference from a
quantitative aspect
.

Pot a s s i u m K r y p t o n

In the fourth period

we meet at rst elements which resemble chemically those at the
begi nning o f the two previous periods This is also what we should
expect We must thus assume tha t the 19 th e lectr on is bound in
a new type of orbit a n d a closer consideration shows that this will
be a 4 orbit The points w hich were em ph asized in connection
with the binding o f the last electron in the sodium atom will be
even more marked here on account o f the larger quantu m number
by which the orbits of th e inner electrons are c h aracterized I n
fact in the p otassium atom the 4 orbit of the 19 th electron will
as far as inner loops are co ncerned coincide closely with the shape
of a 3
orbit O n this account therefore the dimensions of th e
out e r part of the orbit will not only deviate greatly from the
dimensions of a 4 orbit in the hydrogen atom but will coincide
Fo u r t h P e r i o d

PHY S I CAL AND C H E M I CA L PROP E RTI ES OF T HE E L EME N T S

10 1

closely with a hydrog e n orbit of the type

the dimensions of
which are about four times smaller than the 4 hy d rogen orbit
This result allows an immediate explanation o f the main features of
th e chemical properties and the spectrum of potassium C orre
results
apply
t
o calcium in the neutra l atom of which
s on di n
p
g
there will be t w o valency electrons in equivalent 4 orbits
A fter calcium the properties of the eleme n ts in the fourth period
of the periodic system deviate ho w ever more and more from the
corresponding elements in the previous p e riods until in the family
of the iron metals we meet elements whose properties are e s s e n ti
ally di fferent P roceeding to still higher atomic numbers we again
meet di fferent conditions Thus we nd in the latter part of the
fourth period a series O f elements whose chemical properties approach
more and more to the properties o f the elements at the end
o f the preceding periods until nally with atomic number 3 6 we
again meet one o f the inactive gases namely krypton This is
exactly what we Should expect The formation and stability of the
atoms of the elements in the rst three periods require that each
of the rst 18 electrons in the atom shall be b ound in each s u c
c e ed i n
element
in
an
orbit
of the same principal quantum number
g
as that possessed by the particular electron when it rst appeared
I t is readily seen that this is no longer the case for the 19 th
electron With increasing nuclear charge a nd the consequent
decrease in the di fference between the elds of force inside and
outside the region of the orbits of the rst 18 bound electrons the
di mensions of those parts of a 4 orbit which fall outside will
approach more a nd more to the dimensio n s of a 4 quantum orbit
calculated on th e assumption that the interaction between the
electrons in the atom may be neglected Wi th i ncr ea s i ng a tomi c
nu mber a p oi nt w i ll ther efor e be r ea ched w her e a 3 or bi t w i ll cor r e
r m er bi nd i n
s p ond to a
h
1
h
l
a 4 or bi t and
n
h
n
t
r
a
t
o
t
e
9
e
ec
o
t

g f
this occurs as early as at the beginnin g of the fourth period This
can not only be anticipated from a si mple calculation but is conrmed
i n a striking way from an examination of the series spectra While
the Spectrum of potassium indicates that the 4 orbit corresponds
t o a binding which is more than twice as rm as in a 3 orbit
corresponding to the rst Spectral term in the D series the con
d i t i ons are e ntirely di fferent a s soon as ca lci u m is reached W e
,

T HE S T RUC T UR E OF T HE A T O M AND THE

10 2

shall not consider the arc Spectrum which is emitted during the
capture O f the 20 th electron but the spark spectrum which corre
While
the
s on d s t o the capture and binding of the 1 9 th electron
p
Spark spectrum of magnesium exhibits great similarity with the
sodium Spectrum as regards the values of the spectral terms in th e
various series apart from the fact that the constant appearin g in

formula ( 12) is four times as large as the Rydberg constant w e

me e t in th e spark spectr u m of calci u m the remarkable conditio n
.

F ig

that the rst term of th e D series is larger than the rst term of
th e P series and is only a little smaller than the rst term of the
S series which m a y be regarded as corresponding to the binding
of the 1 9 t h electron in the normal state of the calcium atom
These facts are shown in gure 4 which gives a survey of th e
stationary states corresp onding to the arc spectra of sodium a nd
potassium AS in gures 2 and 3 of the sodium spectrum we
h ave disregarded the complexity o f the spectral terms and the
num b ers characterizing the stationary states are simply the quantum
,

PHY S I CAL AND CH EM I CAL PR O P E R TI ES OF T HE E L EME N T S

103

numbers n and h For t h e sake of comparison the scale in which th e

energy of th e di fferent states is indicated is chosen four times a s
small for the spark spectra as for the arc spectra C onsequently
the vertical lines indicated with various val u es of n correspond for
the arc spectra to the spectral ter m s of hydrogen for the Spa rk
spectra to the terms of the helium spectrum given by formula
C omparing the change in the relative rmness in the bindi ng of
the 19 th electron in a 4 and 3 orbit for potassium a nd calcium w e
s ee that w e must be prepared already for the next element
scandium to nd that the 3 orbit will correspond t o a stronger
bin ding of this e lectron than a 4 orbi t O n t h e other h a nd it
follows from pre vious remarks that the binding will be much lighter
than for the rst 18 electrons which agrees that in chemical c om
b i na ti ons scandium appears e le c t r Op os i ti v e ly with three valencie s
If we proce e d to the following elements a s t ill larger number of
3 orbits will occur in the normal state of these atoms since the
number of such el e ctron orbits will depend u pon the rmness of
their b inding compared to the rmness with which an electron is
bound in a 4 orbit in w h ich type of orbit at le as t the l a st captur e d
electron in the atom may be assumed to move We th e refore me e t
conditions which are essentially di fferent from thos e w hich we have
co nsidered in connection with the previous periods s o that h e re
we have to do with the s u cces s i ve d evel op ment of one of the i nner
r ou s o electr ons i n the a tom in this case with groups of el e ctrons
p
f
g
in 3 quanta orbits O nly when the development of this group h a s
b een completed may we expect to nd once more a corresponding
change in the properties of the elements with incre a si n g atom i c
number such a s we nd in the preceding periods The properties
of the elements in the latter part o f the fourth period Sho w
immediately that the group when completed will possess 18
electrons Thus in krypton for e x ample we may expect besides
the groups of 1 2 a nd 3 quanta orbits a m arkedly symmetrical
conguration of 8 electrons in 4 q uanta or bits consisting of four 4
orbits and four 4 orbits
The ques tion now arises :In which way will the gradual forma
tion of the group of electrons having 3 quanta orbits take pl a ce !
From analogy with the constitution of the groups of electrons with
2 quanta orbits we might at rst sight be inclined to suppose that
.

T H E S T R U C T UR E

10 4

OF

THE

A TO M AN D T H E

the complete group of 3 quanta orbits would consist of three su b

groups of four electrons each in orbits of the types
3 and 3
re spectively so that the total number of electrons would be 12
instead of 18 F urther consideration shows howeve r that such an
expectation would not be j ustied The stability of the c ongur a
tion of eight electrons with 2 quanta orb its occu rring in neon must
be ascribed not only to the symmetrical conguration of the elec
tr oni c orbits in the two subgroups of 2 and 2 orbits re s pectively
but fully as much to the possibility of bringing the orbits inside these
subgroups into harmonic relation with on e another The Situation
is di fferent however for the groups of electrons with 3 quanta
orbits Three subgroups of four orbits each can not in this case b e
expected to come into i nteractio n with one another in a corre
s on d i n l
simple
manner
O
n
the
contrary
we
m
u st assume that
p
gy
the presence of electrons in 3 orbits will diminish the harmony of
the orbits with i n the rst two 3 quanta subgroups at any rate
when a point is reached wh ere the 19 th electron is no longer as
was the case with scandium bound considerably more lightly than
the previously bound electrons in 3 quanta orbits but has bee n
drawn s o far into the atom that i t revolves within essentially
the sa me region of the a t o m where these electrons move We
shall n o w assume that this decrease in the harmony will s o to

open
the
previously
closed
conguration
of electrons
sa
y
in orbits of these types AS regards the nal result the number
18 indicates that aft er the group is nally formed there will
be three subgroups containing S i x e l ectrons each E ven if it has
not at prese n t been possible to follow in detail the various
steps in the formation O f the group this result is nevertheless
conrmed in an interesting manner by the fact that it is possible
to arrange three congu rations having s i x electrons each in a Simple
m anner relative to one another The conguration of the subgroups
does not exhibit a tetrahedral symmetry like the groups of 2 quanta
orbits in carbon but a symmetry which s o far as the relative
orientation of the normals to the planes of th e orbits is c on
cerned may be described as trigonal
I n spite of th e great difference in the properties of the elements
o f this period compared with those o f the preceding period the
completion of the group O f 18 electrons in 3 quanta orbits in the
-

PHY S I CAL AND CH EM I CAL PROP E R T I ES OF T HE E LEME N T S

105

fourth period may to a certain extent be said to have the same

c harac teristic results as the completion of the group of 2 quanta
orbits in the second period A s we have seen this determined not
only the properties o f neon as an inactive gas but in addition the
electronegative properties of the preceding elements and the
electropositive properties of the elements which follow The fact
that there is no inactive gas possessing an outer group of 18
electrons is very easily accounted for by the much larger dimensions
which a 3 orbit has in comparison with a 2 orbit revolving in the
same eld of force O n this account a complete 3 quanta group
can not occur as the outermost group in a neutral atom but only
in positively charged ions The characteristic decrease in valency
which we meet in copper Shown by the appearance of the s i ngly
charged cuprous ions indicates the same tendency towards the
completion o f a symmetrical conguration of electrons that we
found in the marked electronegative character of an element like
uorine D irect evidence that a complete group of 3 quanta orbits
is present in the cuprous ion is given by the spectrum of copper
which in contrast to the extremely compl icated spectra of the
preceding elements resulti ng from the unsymmetrical character of
the inner system possesses a Simple structure very much like t hat
This may no doubt be ascribed to a
o f the sodium spectrum
simple symmetrical structure present in the cuprous ion similar to
that in the sodium ion although the great difference in the con
s t i t u t i on o f the outer group of electrons in these ions is Shown
both by the considerable di fference in the values of the spectral
terms and in the separation of the doublets in the P terms of the
two spectra The occurrence of the cupric compo unds shows ,how
ever that the rmness of binding in the group of 3 quanta orbits
in the copper atom i s not as great as the rmness with w hich the
electrons are bo und in the group of 2 q uanta orbits in the sodium
ato m Zinc w hich is always divalent is the rst element in which
the groups of the electrons are so rmly bound that they can not
be removed by ordinary chemical processes
The picture I have given of the formation a nd structure of the
atoms of the elements in the fourth period gives an explanation of
the C hemical and spectral properties In addition it i s supported
by evidence of a di fferent nature to that which we have hitherto
-

T HE STRUC TUR E OF T HE A T O M AND THE

10 6

used It is a familiar fact that the elements in the fourth period

di ffer markedly from the elements in the preceding periods
partly in their ma gneti c p r op er ti es and partly in the cha r a cter i s ti c
P aramagn etism and colours d o occur
col our s o f their compo u nds
in ele m ents belonging t o the foregoing periods but n ot in simple
compounds where the atoms considered enter as ions Many
elements of the fourth period on the contrary exhib it p a r a ma g
netic properties and characteristic colours even in dissociated
aqueous solutions The i mportance of this has been e m phasized
by La denburg in his attempt t o explain the properties of the
elements in the long periods of the periodic system (s e e p
L angmuir in order to account for the di fference between the fourt h
period and the preceding p e riods simply ass u med that the atom
in addition to t h e l a y e r s of cells containing 8 electrons each possesses
an o u ter layer of cells w ith room for 18 electrons which i s c om
u rg
L
adenb
l
e t e ly lled for the rst tim e in the case of krypton
p
assumes that for some reason or other a n
on the other hand
intermediate lay er is developed between the inner electronic
conguration in the atom appearing already in argon and the
external group of valency electrons This layer commences with
scandi u m and is completed exactly at the end of the family of iron
m e tals In support of this assumption L adenburg not only mentions
the chemical properties of the elements in the fourth period but
also r e fers to the paramagn etism and colours which occur exactly
i n th e elements where this intermediate layer Should be in
d e velopm ent I t is seen that La de nb u rg s ideas exhibit certa i n
formal similarities with the i n terpretation I have given ab ove of
the appearance of the fourth period and it is in t eresting to note that
ou r v iew b ased on a direct investigation of the conditions for the
formation of the atoms enab les us t o understand the r e lation
e mphasized by L adenburg
O ur ordinary electrodynamic conceptions are probably insu fcient
to form a basis for an explanation of atomic magnetism This is
hardly t o be wondered at when we remember that they have n ot
proved adequate to account for the phenomena O f radiation which
are connec ted with the in timate interaction between the electric
and magnetic forces arising from the motion of the electrons In
whatever way these di fculties may be solved it seems Simplest t o
,

P HY SIC A L A N D C H EM IC AL PRO PE R T I E S

OF

TH E

E LEME N T S

10 7

sume that the occurrence of magnetism such as we meet in the

elements of the fourth period results from a l a ck of symmetry in
the intern al structure of the atom thus preventing the magnetic
forces a rising from th e motion of the elec trons fro m forming a
system of closed lines of force running wholly within the atom
While it has been assumed that the ions of the elements in the
previous periods whether positively or negatively charged contai n
congurations of marked symmetrical chara cter we must however
be prepared to encount e r a denite lack of symmetry in the
electronic congurations in ions of those elements with i n the fourth
period which contain a group of electrons in 3 quanta orb its in th e
transition stage between symmetrical congurations of 8 an d 18
electrons respectively A s pointed out by Kossel the experimental
results exhibit an extre me simplicity the magnetic moment of the
ions depending only on the number of electrons in the ion F erric
ions for example exhibit the same atomic magnetism as manganous
ions while manganic ions exhibi t the sam e atomic magnetism as
chromous ions I t is in beautiful agreement with what we have
a ssumed about the struct u re of the atoms o f C opper and zinc that
the magnetism disappears with those ions containing 28 electrons
which as I stated must be assumed to contain a complete group
of 3 quanta orbits
O n the whole a consideration of the magnetic
properties of the elements within the fo urth period gives us a vivid
impression of how a wound in the otherwise symmetrical inner
struct ure is rst developed and then healed as we pass from element
t o element It is t o b e hoped that a fu rther inv e stigation of the
m a gnetic properties will give us a clue to the way in which the
group of electrons in 3 quanta orbits is developed step by s tep
A lso the colours of the ions directly support ou r vie w of ato mic
struc ture A ccording to the postulates of the quantum theory
absorption as well as emission of radiation is regarded as taking
place during transitions between stationary states The occurrence
of colours that is to s a
a b s or t i O
the
light
in
the
visible
region
n
o
f
y
p
of the spectrum is evidence of transitions involving energy changes
of the same order of magnitude as those giving the usual optical
spectra of the elements In contrast to the ions of the elemen ts of
the preceding periods where all the electrons are assumed to be very
rmly bound the occurrence of such processes in the fourth period
as

T HE S T RUC TUR E OF T HE AT O M AND T HE

10 8

is exactly what we Should expect F or the development and com

l
e t i on of the electronic groups with 3 quanta orbits will proceed
p
of
in
competition
with
the
binding
of
electrons
in
orbits
s o to s a
y
higher quanta Since the binding of electrons in 3 quanta orbits
occurs when the electrons in these orbits are bound more rmly
than electrons in 4 orbits The development of the group will
therefore proce e d to the point where we may s a y there is e q ui li
This condition may be
b r i u m between the two kinds of orbits
assumed to be intimately connected not only with the colour of the
ions but also with the tendency of the elements to form ions with
d i fferent valencies This is in contrast to the elements of the rst
periods where the charge of the ions in aqueous solutions is always
the same for one and the same element
.

Fi fth P e r i o d

Ru b i d i u m X e n o n

The structure of the atoms

in the remaining periods may be followed up in complete analogy
with what has already been said Thus we s hall assume that th e
3 7 th and 3 8 th electrons in the elements of the fth period are
bound in 5 orbits This is supported by the measurements of the
arc spectrum o f rubidium and the Spark spectrum of strontium
The latter spectrum indicates at the same time that 4 orbits will
soon appear and therefore in this period which like the 4 th
contains 18 elements we must assume that we are witnessing a
fur ther s ta ge i n the develop ment of the electr oni c g r oup of 4 qua nta
The rst stage in the formation of this group may be said
or bi ts
t o have been attained in krypton with the appearance o f a s y m
metrical conguration O f eight electrons consisting of t wo subgroups
each o f four electrons in 4 and 4 orbits A second preliminar y
completion must be regarded as having been reached with the
appearance of a symmetrical conguration of 18 electrons in the
case of Silver consisting of three subgroups with Six electrons each
in orbits of the types
4 and 4
E verything that has been s a id
about the successive formation of the group of electrons wi th 3
quanta orbits applies unchanged to this stage in the transformation
of the group with 4 quanta orbits
F or in no case have we m a de
u s e of the absolute values of the quantum nu mbers nor o f a s s u m
p
tions concerning the form of the orbits b u t only of the nu mb e r O f
possible types of orbits which might com e into consideration A t
.

PHY S I CAL A N D CH EM I CA L P R O P E RT I ES OF T HE E LEMEN T S

10 9

the s a me time it may be of interest to m ention that the properties

o f these elements compared with those of the foregoi n g period
n evertheless show a difference corresponding e x actly to what would
be expected from the di fference in the types of orbits For instance
the divergencies from the characteristic valency conditions of the
elements in the second and third periods appear later in the fth
period than for elements in the fourth period While an element
like titan ium in the fourth period already Shows a m arked tendency
t o occur with various valencies on the other hand an elemen t like
zirconium is still quadri valent like carbon in the second period
and Silicon in the third A Simple investigation of the kinematic
properties of the orbits of the electrons shows in fact that an
electron in an excentric 4 orbit of an element in the fth
period will be considerably more loosely bound than an electron i n
a circular 3 orbit of the correspondi n g element in the fourth
period w hile electrons which are bound in e x centric orbits of the
types 5 and 4 respectively will correspon d to a bin ding of about
the same rmness
A t the e n d of the fth period we may assume that xenon the
atomic number of which is 5 4 has a structure which in addition to
the two I quantum eight 2 quanta eighteen 3 quanta and eight
teen 4 quanta orbits already mentioned contains a symmetrical
conguration of eight electrons in 5 quanta orbits co n sisting of two
subgroups with four electrons each in 5 and 5 orbits respectively
.

e s i u m N i t o n If we n ow consider the atoms

we must rst of all
of elements of still higher atomic number
ass u me that the 5 5 th and 5 6 t h electrons in the atoms o f c aesiu m
and barium are bound in 6 orbits This is conrmed by the spec t ra
It is clear however that we must be prepared
o f these elements
shortly to meet entirely new conditions With increasing nucle a r
charge we shall have t o expect n o t only that an electron in a 5
orbit will be bound more rmly t ha n i n a 6 orbit but we must also
expect that a moment will arrive when during the formation of the
atom a 4 orbit will represent a rmer b inding of the electron than
an orbit of 5 or 6 quanta in much the same way as in the elements
of the fourth period a new stage in the development o f the 3 quanta
group was started when a point was reached where for the rst
S i x th P e r i o d

Ca

T HE S TRUC T UR E OF THE AT OM AND T HE

110

time the 19 th electron was bound in a 3 orbit instead of in a 4

orbit We shall thus expect in the sixth period to meet with a new
stage in the development of the group with 4 quanta orbits O nce
this point has been reached we must be prepared t o nd with i n
creasing atomic number a number of elements following one another
which as in the family of the iron metals have very nearly the same
properties The similarity will however be still more pronounced
since in this case we are concerned with the successi ve transforma
tion o f a conguration o f electrons which lies deeper in the interior
of the atom Y ou will have already guessed that what I have in View
is a simple explanation of the occurrence O f the fa mi ly of r a r e ea r ths
at the beginning of the sixth period AS in the case of the transforma
tion and completion of the group of 3 quanta orbits in the fourth
period and the partial completion of groups O f 4 quanta orbits i n
the fth period we may immediately deduce from the length of the
sixth period the number of electrons namely 3 2 which are nally
contained in the 4 quanta group of orbits Analogous to what
applie d to the group of 3 quanta orbits i t is probable that when
the group is complete d it will contain eight electrons in each of the
four subgroups E ven though it has n ot yet been possible to follow
the development of the group step by step we can even here give
some theoretical evidence in favour of the occurrence of a sym
metri cal conguration of exactly this number of electrons I shall
simply mention that it is not possible without coincidence of the
planes of the orbits to arrive at an interaction between four s ub
groups O f s i x electrons each in a conguration of simple trigonal
symmetry which is equally simple as that Shown by three subgroups
The difc u lties which we meet make it probable tha t a harmo nic
interaction can be attained precisely by four groups each containing
eight electrons the orbital congurations of which exhibit a x ial
symmetry
Just as in the case of the family of the iron metals in the fourth
period the proposed explanation of the occurrence of the family of
rare earths in the sixth period is supported in an interesting
manner by an investigation of the magnetic properties of these
elements In spite of the great chemical Similarity the members
O f this family exhibit very di fferent m agnetic properties S O tha t
while some o f them exhibit but very little magnetism others exhibit
,

P HY SIC AL A N D C H E MIC AL PR O PE R T I E S

O F TH E

E LEME N TS

III

a greater magnetic moment per atom than any other element which
has been investigated I t is also possible t o give a simple i n t e r pr e
t a ti on o f the peculiar colours exhibited by the compounds of these
elements in much the same way as in the case of the family of iron
metals in the fourth period The i dea that the appearance of the
group of the rare earths is connected with the development of inner
groups in the atom is not in itself new and has for instance been
considered by Ve ga r d in connection with his work on X ray spectra
The new feature of the present considerations lies ho wever in the
emphasis laid On the pec uliar way in which the relative strength of
the bindi ng for two orbits of the same principal quantum number
but O f di fferent shapes varies with the nuclear charge and with the
number of electrons previously bound D u e to this fact the presence
O f a group like tha t of the rare earths in the sixth period may be
considered as a direct consequence o f the theory and might actually
have b een predicted on a quantum theory adapted to the explana
tion of the properties of the elements within the preceding periods
in the way I have sho wn
Besides the na l devel op ment of the gr oup of 4 qua nta or bi ts we
observe in the sixth period in the family O f the platinum metals the
h
u a n ta or bi ts
t
e g r ou
o
5
s econ d s ta ge i n the d eve lop ment o
f
p f
q
A lso in the radioactive chemically inactive gas niton which com
pletes this period we O bserve the rst preliminary step in the
development of a group of electrons with 6 quanta orbits In the
atom of this element in addition to the groups O f electrons of two
1 quantum eight 2 quanta eighteen 3 quanta thirty two 4 quanta
and eighteen 5 quanta orbits respectively there is al so an outer
symmetrical conguration of eight electrons in 6 quanta Orbits
which we shall assume to consist of tw o subgroups with four electrons
each in 6 and 6 orbits respecti v ely
.

S e v e n th P e r i o d

In the seventh and las t period of th e periodic

system we may expect the appeara nce of 7 quanta orbits in the
normal state of the atom Thus in the neutral atom of radium in
addition to the electronic structure of niton there will be t w o
electrons in 7 orbits which will penetrate during their revolution
not only into the region O f the orbits of electrons possessing lower
v a lues for the principal quantum n u mber b u t ev e n t o distances
.

THE S T RUC T UR E OF T HE A T O M AND T HE

1 12

from the n u cleus which are less than the radii of the orbits of the
inn erm ost I quantum orbits The properties of the elements in th e
seventh period are very Similar to the properties of the elements in the
fth period Thus in contrast to the conditions in the Sixth period
there are no elements whose proper ties resemble on e another lik e
those of the rare earths In exact analogy with what has already
been said about the relations between the properties of the elements
i n the fourth and fth perio d s this may be very simply explained b y
t h e fact that an excentric 5 orbit will correspond to a considerably
looser binding of an electron in the atom of an element of t h e
seventh period than the binding of an electron in a circular 4 orbi t
in the correspondi ng element of the sixth period whi l e there will be
a much smaller difference in the rmness of the binding of thes e
electrons in orbits of t he types 7 and 6 respectively
I t is well known that the seventh period is not complete for no atom
has been found having an atomic nu mber greater than 9 2 This i s
probably connected with the fact that the last elements in the
system are radioactive and that nuclei of atoms with a total charge
2
f
reater
than
will
not
be
suf
iciently
stable
to
exist
under
9
c on
g
I t is tempting to
d i t i on s where the elements can be O bserved
sketch a picture of the atoms formed by the capture and binding
and thus to
o f electrons around nuclei having higher charges
obtain some i d ea o f the properties which the corresponding hypo
thetical ele m ents might be expected to exhibit I shall n ot develop
this m atter further however since the general results we should
get will be evident to y ou from the views I have developed to
explain the properties of the elements actually O bserved A survey
of th e se results is given in the following table which gives a s m
y
b ol i c a l rep r esentation of the atomic structure of the inactive gases
In
w hich complete the rst s i x pe ri ods in the periodic system
order to e m phasize the progressive change the table i ncludes the
probable arrangement of electrons in the next atom which would
possess properties like the inactive gases
The view of atomic cons t itution underlying this table which
involves con gura t ions of electrons moving with large velocities

between each other s o that the electrons in the outer groups

penetrate into the region of the orbits of the electrons of the inner
r oups is of co u rse completely di fferent from such statical mod els
g
-

PHY SI CAL AND CH EM I CA L PROP E RTI ES OF T HE E L EMEN T S

113

the a tom as are proposed by Langmuir But quite apart from this
it will be seen that the arrangement of the electronic groups in
the atom to which we have been lead by tra c ing the way in which
each single electron has been bound is essentially di fferent from
the arrangement of the groups in L angmuir s theory In order t o
explain the properties of the elements of the Sixth period L angmuir
assumes for instance that in addition to the inn e r layers of cells
c onta ining 2 8
8 18 and 18 electrons respectively which are
e mployed to account for the properties of the elements in th e
earlier periods the atom also possesses a layer of cells with room
for 3 2 electrons which is j ust completed in the case of niton
of

In this connection it may b e of interest to mention a recent

paper by Bury to which my attention w a s rst drawn after the
deliverance of this address and which contains an interesting
surv ey of the chemical properties of the elements based on similar
c onceptions of atomic structure as those applied by L ewis and
L angmuir From purely chemical considerations Bury arrives at
conclusions which as regards the arrangement and completion of
the groups in the main coincide wit h those Of the present theory
th e outlines of which were given in my letters to N a tur e mentioned
in the introduction
,

S u rv e y

th e p e ri od i c t a b l e

The results given in this add r ess

are also illustrated by means O f the representation o f the periodic
system given in g 1 In this gure the frames are meant to

indicate such elements in which one of the inner groups is

in a stage of development Thus there will b e found in th e
of

T HE S TRUC T UR E OF T HE A T O M AND T HE

114

fo u rth

and fth periods a Single frame indicating the nal com

l
e t i on of the electronic group with 3 quanta orbits
and
the
p
l as t stage b u t on e in the development of the group wi t h 4 quanta
I n the Sixth period it has been necessary t o
Orbits respectively
introd u ce two frames o f which the inner one indicates the last
s tage o f the evolution o f the group with 4 quanta orbits giving rise
to the rare earths This occurs at a place in the periodic syste m
Where the third stage in the development of an electronic group
with 5 quanta orbits indicated by the outer frame has already
b e gun In t h is connection it will be seen that the inner frame
e n closes a smaller number of elements than is usually attributed
t o the family o f the rare earths
A t the end of this group an
uncertainty exists due to the fact that no element of atomic
n u mber 7 2 is kno wn with certainty H owever as indicated i n
g 1 we must conclude from the theory that the group with
4 quant a orbits is nally completed in lu tetium
Th I S ele m en t
therefore o ught to be the last in the seque n ce of consecutive
e lemen ts wi t h similar properties in the rst half of the Sixth period
a nd a t t he place 7 2 an element must be expected which in its
c hemical and physical properties i s homologous with zirconium and
This which is already indited on Julius Thomsen s old
t horium
table has also been pointed out by Bury !Quite recently D a u v i lli e r
ha s in an investigation o f the X ray spectrum excited in preparations
c ontaining rare earths observed certain faint lines which he ascribes
t o a n element of ato m ic number 7 2 This element is identied by
him as the el e ment celtium belonging to the fam ily O f ra re earths
the existence of which had previously been suspected by U rbain
uite
part
fro
the
d
ifcul
ies
which
this
result
if
correct
might
m
t
a
Q
e ntail for atomic theories it would Since the rare earths according
to chemical vie w possess three valencies imply a rise in positive
valency o f tw o units when passing from the element 7 2 to the
n e x t element 7 3 tantalum This would mean an exception fro m
th e otherwise general rule that the valency never increases by
m ore than one unit when passing from one element to the ne x t in
th e periodic table ! In the case of the incomplete seventh period
t he full drawn frame in d icates the third stage in the developme nt
Of the electronic group with 6 quanta orbi t s which must begin in
a ctinium
The dotted frame in d icates the last stage but one in
-

the development of the group with 5 quanta orbits which hitherto

has not bee n Observed but which ought to begin shortly aft er
uranium if it has not already begun in this element
With reference to the homology of the elements the exceptional
position of the elements enc losed by frames in g 1 is further
emphasized by taki ng care that in spit e of the large Similarity
many elements exhibit no connecting lines are drawn between
two elements which occupy different positions in th e system with
respect to framing In fact the large chemical similarity be tween
for instance alumi nium and scandium both O f which are trivalent
and pronounced electropositive elements is directly or indirectly
e mphasized in the current repres entations of the periodic table
While this procedure is j ustied by the analogous structure of the
trivalent ions of these elements ou r more detailed ideas of a tomic
structure suggest however marked di fferences in the physical
properties of alu minium and scandium originating in the e s s e n t i
ally di fferent character of the way in which the last three electrons
in the neutral atom are bound This fact gives probably a direc t
explanation of the marked di fference existing between the spectra
E v en if the spectrum of scandium is
of aluminium and scandium
n ot y e t sufciently cleared u p this di fference seems t o b e of a much
more fundam e ntal character than for instance the difference between
the arc spectra O f sodium and copper which apart from the large
di fference in the absolute values of the spectral terms possess a
completely analogous structure as previo u sly mentioned in this
essay O n the whole we must expect that the spectra of elements
i n the later periods lying inside a frame will Show new features
compare d with the spe ctra of the elements in the rst three periods
This expectation seems supported by recen t work on the spectrum
O f mangan ese by C atal an which appe a red j us t before the printing
of this essay
Before I leave the int e rpretation of the chemical prope rties by
m e a n s of this a tomic model I s houi d like to remind y ou once again
O f the fundamental principles which we have used The whole
th e ory has evolv e d from an investigation of the w a y in which
e lectrons can b e capt u red by an at om The formation of an atom
w as held t o consist i n the successive b in ding of electrons this
b in di ng res u lti ng in radiation accordi n g t o th e quan t u m th e ory
-

T HE S TRUC TUR E OF T HE A T OM AND T HE

1 16

A ccording to the fundamental postulat e s of the theory this binding

takes place in stages by transitions between stationary states
accompanied by emission of radiation F or the problem of the
stabili ty of the atom the essential problem is at what stage such a
process comes to an end A s regards this point the postulates give
n o direct information but here the correspondence principle is
brought in E ven though it has been possible to penetrate con
further
at
many
points
than
the
time
has
permitted
me
s i d e ra b l
y
to indicate to y ou still it has n ot y e t been possible to follow in
detail all stages in the formation of the atoms We cannot say for
instance that the above table of the atomic constitution of the
inert gases may in every detail b e considered as the unambiguous
res u lt of applying the correspondence principle O n the other hand
i t appears that ou r considerations alrea dy place the empirical data
in a light which scarcely permits of an essentially di fferent interpreta
tion O f the properties of the elements b ased upon the postulates of
the quan t um theory This applies not only to the series Spectra
and the clos e relationship of these to the chemical properties of the
elements but also t o the X ray spectra the consideration of which
leads u s in to an investigation of i n teratomic processes of an entirely
di fferen t C haracter A s we have already mentioned it is necessary
to assume that the e mission of the latter spectra is connected with
processes which may be described as a reorganization of the com
l
ete l
formed
atom
after
a
distur
b
ance
prod
u
ced
in
th
e
interior
p
y
of the atom by the action of external forces
_

IV

REO R! A N I Z AT I ON O F A T O M S A N D X RAY S PE CT R A
-

in the case of t h e series spectra it has also bee n possible to r e pr e

sent the frequency Of each line i n the X ray spectrum O f an element
as the di fference of two of a s e t of spectral terms We Shall there
fore a ssume tha t each X ray line is due to a transition between
t w o stationary states of the ato m The val u es of the atomic energy
corresponding to these states are freq u ently referred to as the

energy levels O f the X ray spectra The great d i fference b etween

the origin o f the X ray and the series spectra is clearly seen how
ever i n the di fference of the laws applying to the absorption O f
radiation in the X ray and the optical regions of the spectra The
ab sorptio n by non exci ted a toms in th e latt e r case is connected
AS

PHY SIC AL A N D C HE MI C AL P R O PER T I E S

O F TH E

E LEME N TS

117

with those lines in the series sp e ctrum which correspond to com

b i na ti ons of the vario u s spectral terms with the largest of these
terms A s has been shown especially by the investigations of
Wagner and de Broglie the absorption in the X ray region on
the other hand is connected not with the X ray lines but with

ce rtain spectral regions commencing at the S O called absorption

edges The frequencies of these e dges agree very closely with the
spectral terms used t o account for the X ray lines We shall now
s e e how the conception of atomic structure developed in the pre
ceding pages O ffers a simple interpretation of these facts L et us
consider the following ques tion What changes in the state O f the
atom can be produc e d by the absorption of radiation and which
processes of emission can be initiated by such changes !
,

Ab s o r p t i o n

e m i s s i o n o f X r a y s a n d c or r e s p o n d e n c e
f
o
r
n
The
possibility
producing a change at all in the
i
i
l
e
c
p
p
motion of an electron in the interior of an atom by means of radia
tion must in the rst place be regarded as intimately connected
with the character of the interaction between the electrons within
the separate groups In contrast to the forms of motion where at
every moment the position of the electrons exhibits polygonal or
polyhedral symmetry the conception O f this interaction evolved from
a consideration of the possible formation of atoms by successive
b inding Of electrons ha s such a character that the harmonic com
on e n t s in the motion o f an electron are in general represented in
p
the resulting electric m oment of the atom As a result of this i t
will be possible t o release a Si ngle electron from the interaction
with the other electrons in the same group by a p r oc es s w hi ch
possesses the necessary analogy with an absorption process on
the ordinary electrodynamic vie w claimed by the correspondence
principle The points of view on which we based the interpreta
tion of the development and completion of the groups during the
formation of an atom i mply on the other hand that j ust as n o
additional electron can be taken up into a previously completed
group in the atom by a change involving emission of radiation
Similarly it will n ot be possible for a new electron to b e added
to such a group when the state of the atom is changed by
absorption O f radiation This m e ans that a n electron which b elongs
and

T HE

1 18

S TRUC TUR E OF THE A TOM AND T HE

to one of the inner groups of the atom as a consequence of an

absorption process besides the case where it leaves the atom
completely can only go over either to an incompleted group or
to an orbit Where the electron durin g the greater part of its r e v olu
tion moves at a distance from the nucleus large compared to the
distance of the other electrons O n account of the peculiar conditions
of stability w hich control the occurrence O f incomplete groups in
the interior of the atom the energy which is n ecessary to bring
about a transition to such a group wi ll in general di ffer very little
from that required to remove the particular electro n completely
from the atom We must therefore assume that the energy level s
corresponding to the absorption edges in dicate to a rst a ppr oxi
mation the amoun t of work that is required to remove an electron
in one of the inner groups completely from the atom The
correspondence principle also provid e s a b a sis for u nderstanding
the experimental evidence about the appearance o f the emissio n
lines O f the X ray Spectra due to transitions between the stationary
states corresponding to these e nergy levels Thus the n a ture of the
interaction between the electrons in the groups of the atom implies
that each electron in the atom is s o to s a y prepared independen tly
of the other electrons in the same group to seize any opportunity
which is o ffered to become more rmly bound by being taken up
into a group of electrons with orb its corresponding to smaller values
o f the principal quantum number
It is evident however that on
the basis O f ou r views O f atomic structure such an opportunity i s
always at hand as soon as an el e ctron has b een removed from one
of these groups
A t the same time that ou r vie w of the atom leads to a natural
conception of the phenomen a of emission and absorption of X ray s
agreeing closely with that by which K ossel has attempted t o give
a formal explanation O f the experimental O bservations it also suggests
a simple explanation of those quanti tative relations holding for the
frequencies of the lines which have been discovered by Moseley and
S ommerfeld These researches brought to light a remarkable and
fa r reaching similarity between the Rontgen spectrum of a given
element and the spectrum which would be expected to appear upo n
the binding of a single electron by the nucleus This similarity we
imm e diat e ly understand if we recall that in the normal state of the
,

'

PH Y SI C AL

AN D C H EM I CAL P R O P E RT I ES

TH E

OF

E L EME N T S

119

atom there are electrons moving in orbits which with certain

limi tations correspond to all stages of such a bindi ng process and
that when an electron is removed from its original pl ace in the
atom processes may be started within the atom which will corre
s ond to all transitions between these stages permitted by the
p
correspondence principle This brings us at once ou t of tho s e
difculties which apparently arise when one attempts t o a ccoun t
for the origin of the X ray spectra by means of an atomic structure
suited to explain the periodic system This di c u lty has been fe lt
t o such an extent that it has led S o m merfeld for example in his
recent work to assume that the congurations of the electrons in
the various atoms of one and the same element ma y be di fferen t
even under usual conditions S ince in contrast to ou r idea s he
supposed all electrons in the principal groups of the atom to mov e
in equivalent orbits he is compelled t o assume that these grou ps
are di fferent in the different atoms correspondi n g t o di ff erent
possible types of orbital shapes S uch an a s s u mp ti on h o we v e r seems
inconsis tent with an interpretation of the denite character of th e
physical and chemical properties of the elements a nd stan d s in mark e d
contradiction with the points of view about the stability of th e atom s
which form the b asis of the view of a tomic structure here propos e d
,

e c t r a a n d a t om i c s tr u c t u r e In this connec tion it is

o f interest to e mphasize that the group distrib u tion of the e lectro n s
in the atom on which we have based both the explanation of th e
periodic system and the classication of the lines in the X r a y
spectra s hows itself in an entirely different manner in these two
phenomena While the characteristic change of the c hemica l
properties with atomic number is due to the gradual development
and completion of the g roups of the looses t bound electrons the
characteristic absence of almost every trace of a periodic change in
the X ray spectra is due to t w o causes Firstly the electronic
conguration of the completed groups is repeated unchanged for
increasing atomic number and secondly the gradual way in which
the incompleted groups are developed implies that a type o f orbit
from the moment when it for the rst time appears in the normal
s tate of the neu tral atom al w ays will occur in this state and wil l
correspond to a steadily increasing rmness of bi nding The develop
X

ray s p

T HE ST RUC T UR E OF T HE AT OM AND T HE

120

ment of the groups in the atom with increasing atomic number

which governs the chemical properties of the elements shows itself
in the X ray spectra mainly in the appearance of new lines S w i nn e
h as already referred to a connection of this kin d between the periodic
system and the X ray spectra in connection with K ossel s theory
We can only expect a closer connection bet ween the X ray pheno
mena and the chemical propert ies of the elements when t h e con
d i t i on s on the surface of the atom are concerned In agreement
with what has been brought to light by investigations on a b s or p
tion of X rays in elemen ts of lower atomic number such as have
been performed in recent years in the physical laboratory at L und
we understand immediately that the position and eventual stru e
ture of the absorption edges will to a certain degree depend upon
t h e physical and chemical conditions unde r which the element
investigated exists while such a dependence does not appear in
the characteristic emission lines
If we attempt to obtain a more detailed explanation of the
e xperimental O bservations we meet the question of the inuence
of the presence of the other electrons in the atom upon the rmness
This inuence
o f the binding of an electron in a given type of orbit
will as we at once s e e be least for the inner parts o f the atom
where for each electron the attrac tion of the nucleus is large in
proportion to the rep ulsion of the other electrons It should also
be recalled that while the relative inuence of the presence of the
other electrons upon the r mness of the binding will decrease with
increasing charge of the nucleus the e ffect of the variation in the
mass of the electron with the velocity upon the rmness O f the
binding will increase strongly This may be seen from S ommerfeld s
formula
While we O btain a fairly good agreement for the
levels corresponding to the removal of one of the innermost electrons
in the atom by using the simple formula
it is however already
necessary to take the inuence of the other electrons into considera
t i on i n ma k i ng a n approximate calculation o f the levels corresponding
to a removal of an electron from on e of the outer groups in the
atom Just this circumstance O ffers us however a possibility of
obtaining information about the congurations of the electrons in
the interior of the atoms from the X ray spectra N umero u s
investigations have b e en directed a t this q u estion b oth by
,

PHY S I CA L A N D CH EM I CA L PRO P E R TI ES OF T HE E L E M E NTS

121

S ommerfeld and his p u pils and by D e bye Ve ga r d and others It

may also be remarked that de Broglie and D a u vi lli er in a recent
paper have tho u ght it possible t o nd support in the experimental
material for certain assumptions about the numbers O f electrons in
the groups O f the atom t o which Da u v i lli er had been led by con
siderations abo u t the periodic system si milar to those proposed by
L angmuir and L adenburg In calculations made in connection with
these investigations it is assumed that the electrons in the various
groups move in separate concentric regions of the atom s o that
the e ffect of the presence of the electrons in inner gro u ps upon the
motion of the electrons in outer gro u ps as a rst approximation
may b e expected to consist i n a Simple screening of the n ucleus
O n ou r view ho wever the conditions are essentially different since
for the calculation of the rmness of the binding O f the electrons
it is necessary to take into consideration that the electrons in the
more lightly bound groups in general during a certain fraction of
their revolution will penetrate into the region of the orbits of
electrons in the more rmly b ound groups O n account O f this
fact many examples O f which we s a w in the series spectra we ca n
n ot expect to give an accoun t of the rmness o f the binding of the

separate electrons simply by means of a screening correction

con sisting in the subtraction O f a constant quantity from the value
for N in such formulae as ( 5 ) and
F urthermore in the cal e u
lation O f the work corresponding to the energy levels we must tak e
acc ount not only o f the interaction between the electron s in the
normal state of the atom but also of the changes in the congu
ration and interaction of the r e maining electrons which establish
themselves automatically without emission of radiation during the
removal of the electron E ven though such calculations have n ot
yet been made very accurately a preliminary investigation has
already shown that it is possible approximately to account for the
experimental results
.

C l a s s i c a t i o n

e c t r a Independently O f a deni te
view of atomic structure it has been possible by means of a formal
application of Kossel s and S ommerfeld s theories to disentangle
the large amount of experimental material on X ray spectra This
m at e rial is drawn m a inly fro m the accurate m e as urements O f
of

ray

sp

'

THE

1 22

S TRUC T UR E OF T HE A T OM AND T HE

S iegb a hn and his collaborators From this disentanglement of the

experimental observations in which besides S ommerfeld and his
students esp e cially S m ek a l and C oster have taken part we have
O btained a nearly complete classication of the energy levels corre
s on di n
to
th
e
X
ray
spectra
These
levels
are
formally
referred
p
g
t o types of orbits characterized by two quantum n u mbers n and lo
and certain denite rules for the possibilities O f com b inatio n
between the vario u s levels hav e also been found In this way a
number of res u lts of great int e rest for the further elucidation of
the origin of the X ray spectra have b een attained F irst it ha s
n ot only been possible t o nd levels which within certai n limits
correspond to all possible p airs of n u mbers for n and lo but it has
been found that in general to each such pair more than one level
m u st b e assigned This result which at rs t may appear very
s u rprising upon further consideration can be given a simple
i n terpretation We must remember that the levels d e pend not
only upon the constitution of th e atom in the normal state b u t
also upon the congurations which appear after the removal
of one of th e inner electrons and which in contrast to the normal
state do not possess a uniquely completed ch a racter If w e thus
consider a proce s s in which on e of the electrons in a grou p
( subgroup ) i s removed we must be prepared t o nd that after the
process the orbits of the remaining electrons in this group may be
orientated i n more than one way in relation t o one another and
still full the co n ditions required of the stati onary states by th e

quantum theory S uch a view of the complexity of the l e vels a s

further con sideration shows j ust a ccounts for th e mann e r i n which
the energy di fference of the two levels varies with the atomic
nu mb er Witho u t attempting to develop a more detailed picture
O f atomic structure S m ek a l has already disc u ssed the possibility
of accounti n g for the multiplicity of lev e ls
B e sides referring t o
the possibility that the separate electrons in the principal groups
d o not move in equivalent orbits S m e k a l suggests the introduction
o f three quantum numbers for the description of the various groups
but does not further indicate to what e xtent these quantum
numbers shall be regarded as characterizing a complexity in the
structure of the groups in the normal state itself or on the
contrary characterizing the incompleted groups which app e ar
w hen an elec t ron is removed
.

P HYSICAL A N D C H EM IC AL PR O PE R TI E S

TH E

OF

E L EME N T S

1 23

It will be s e en that the complexity of the X ray levels exhibits a

close analogy w ith the explanation of the complexity of the terms
of the series spectra Ther e exists however this di fference between
the complex stru cture o f the X ray spectra and the complex
struct u re of th e lines in the series spectra that in the X ray
spectra there occur n ot only combinations between sp e ctral terms
for which It varies by unity b u t also between terms corre
t o be
to
the
same
value
This
may
be
assumed
s ondi n
o
f
k
p
g
d ue t o th e fa ct that in the X ray spectra in contrast to the s e ries
-

N i t on

Fi g 5
.

ectra we have t o d o with transitions between stationary st a tes

where both before a nd after the transition the electron concerned
t a kes part i n an intimate interaction with other electrons in orbits
with the same principal quant um number E ven though this
interaction may be assumed to be of such a nature that the
harmonic components which would appear in the motion of an
electron in the ab sence o f the others will in gen e ral also ap pear
in th e resulting moment of the atom we must expect tha t the
interaction between the electrons will give rise to the appearance
in this moment O f new t es of harmonic c om one n ts

sp

T HE S T RUC T UR E OF T HE AT O M AN D T HE

124

I t ma y be of interest t o insert here a few words abo u t a ne w

paper of C oster which appeared after this address was given
and in which he has succeeded in obtaining an extended and
detailed connection between the X
ray spectra and the ideas
The classication men
of atomic structure given in this essay
t i one d above was based on measurements O f the spectra of the
heaviest elements and the results in their complete form which
were principally due to independent work O f C oster and Wentzel
may be represented by the diagram in g 5 which refers to
elements in the neighbourhood of niton The vertical arrows
,

Xe non

Kryp t on

F ig

represent the O bserved lines arising from com b inations between

the different energy levels which are represented by horizontal lin e s
In each group the levels are arran ged in the same succession as
their energy values but their distances do not give a quan titati ve

picture of the actual energy di fferences since this would require a

much larger gure The numbers n! attached to the di fferent le v els
indicate the type O f the corresponding orbit The letters a and b
refer to the rules of combinatio n which I mentioned A ccording
to these rules the possibility o f combination is limited ( 1) by the
exclusion O f combinations for which It changes by more than one
unit ( 2) by the condition that only combinations between an a
and a b l e v e l can t a k e pl a ce The l a tt e r r u le was give n i n th i s
.

P HY S I CA L

AND CH EM I CA L PR O P E R T I ES OF T HE E L EME N T S

125

form

by C ost e r ; Wentzel formulated it in a somewhat different

w a y by the formal introduction O f a third quantum number In
his new paper C oster has established a similar classi cation for the
lighter elements F or the elements in the neighbourhood of xenon
and krypton he has Obtained results illustrated by the diagrams
given in g 6 Just as in g 5 the levels correspond exactly to
those types O f orbits which as seen from the table on page 113
according to the theory will be present in the atoms of these ele
ments In xenon se veral of the levels present in niton have dis
appeared and in krypton still more levels have fallen away C oster
h a s also investigated in which elements these particular levels
appe a r for the last time when passing from higher to lower atomic
numb e r H is results concerning this poin t conrm in detail the
pr e dictions O f the theory F urt h er he proves t hat the change in
the rmness of binding O f the electrons in the outer groups in
th e elements of the family of the rare earths shows a dependence
on the atomic number which strongly supports the assumption that
in these el e ments a completion of an inner group of 4 quanta
orbits takes place F or details the reader is referred to C oster s
paper in the P hi los op hi ca l M a ga z i ne Another important con
t r i b u ti on to ou r systematic knowledge of the X ray spectra is
contained in a recent paper by Wentzel H e Shows that vari ous
line s which nd no place in the classication hitherto considered
can be ascribed in a natural manner to processes of reorganization
initiated by the removal O f more than one electron from the
atom ; th e se lines are therefore in a certain sense analogous to
the enhanc e d lin e s in the optical Spectra
.

CONCLU S I O N

Befor e b ringin g this address to a close I wish once more t o

emphasize the complete analogy in the application of the
quantum theory t o the stability Of the atom used in explaining
t w o s o di fferent phenomena as the periodic system and X ray
spectra This point is of the greatest importance i n j udging th e
reality of the theory since the j ustica tion for employing con
sid e rations relating t o the formation of atoms by successive capture
o f electrons as a g u iding principle for the inv e stigation of atomic
,

S TRUC TUR E OF T HE AT OM

T HE

126

stru ct u re might appear doub tfu l if s uch co n siderations co u ld not

be brought into natural agreement with views on the r e or ga ni
z a t i on o f the atom after a disturbance in the normal electronic
arrangement E ven though a certain inner consiste n cy in this
view of atomic struc ture w ill be recognized it is how e ver hardly
n ecessary for me t o emphasize the incomplete character of the
theory not only as regards the elaboration of details b ut also s o
far a s the foundation of the general points of View is concerned
There seems however to be no other way of adva nce in atomic
problems than that which hitherto has been follo w ed n amely t o le t
the work in th e se t wo directions go hand in hand
.