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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
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
P R EF A C E
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
P R EF A C E
vii
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
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 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
sp
R
n
1
( )
values
of
th e se wa ve lengths multipli e d by
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
(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
F,
at
1,
2,
2,
1
x
3
( )
O N T HE S PE C TRUM OF HYDROG E N
(
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
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
.
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
ON
THE S PE C T RU M OF HYDR O GE N
ON
T HE S P E C TRUM OF HYDR O G E N
2W
a)
7r e
2a =
4
( )
ON THE S PE C T RU M OF HYDROG E N
10
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
hv = E ,
0r
5
( )
D uring
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
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
Rho
n
L et
let us by way
of
:
i
I /0
experiment put W :
2 B k
i
This gives us
6
( )
mm
ON T HE S PE C T RU M OF HYDR O G E N
13
creases as
71
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
2Rc/n
3
.
27
6 771
n.
ON T HE S P E CT RU M OF HYDROG E N
14
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
Th e P i c k e r i n g l i n e s
Y ou
C0
2 4
6 717
Repeating
2w N
ch
2 4
,
n2
12
(9 )
16
ar
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
"
(E
60
W (M
m)
Mm
2 4
27 1 N
ch
'
mM
2 4
M
(
m)
1
0
( )
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
where M is the
m ass
of the n u cleus
The correction is
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
ON T HE SE R I ES S P E C T RA OF T HE E L EM EN T S
21
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
En
nhw ,
ON T HE SE R I ES S P E C T RA OF T HE E L EME NT S
22
2
( )
a) ,
I
I
A E = hv
3
( )
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
24
ON
T H E S E R I E S SP E C TR A
THE
OF
E LEME N T S
H y d r o ge n
f
( r
5
( )
"
"
7 1 6 777.
ON
25
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
ON THE SE R I ES S P E C TR A OF T HE E LEMEN T S
26
"
"
"
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
20
C OS
27 7
'
m
t
(
1
1
( )
O N TH E S E R I E S SP E C TR A
TH E
OF
E L EME N T S
2W
27
This condition
12
( )
c or
'
O N T HE SE R I ES S P E C T RA OF THE E LEME N TS
28
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
or
occu r r ence
'
a ,
12
'
1
3
( )
to,
ON
29
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
( )
ON T HE SE R I ES S PE C T RA OF THE E L E M E N T S
30
(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 )
ON T HE SE R I ES S P E C T RA OF T HE E L EME N TS
31
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
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
O N TH E S E R I E S S PE C TRA
O F TH E
E LEM EN T S
35
36
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
O N T HE SE R I ES S PE C TRA OF T HE E LEME N T S
37
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
1 27
1 4w
.
6 772
2a n
= n2
27r
cun
z z
i"
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
Th e S t a r k
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
'
E : E,
kh a ,
1
( 9)
7,
1 27 r
3h F
nk
( 20 )
27 r
3h F
( 0)
77
8 77
(
cm
n lc
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
C OS
277
'
TO)
ICO
05
.
12 N
'
"
k
(
a)
2
( 3)
'
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
Th e Z e e m a n
'
4 7t m c
2
4
( )
'
T HE SE R I ES S PE C T RA OF T HE E L EME N T S
ON
43
'
'
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
k
7
of
the orbit
45
of
In the case
a mag
lo
of
a circle
is simply equal to
,,
2p ),
27
2
5
( )
6 771
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
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
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
Th e o r y
O N TH E S E R I E S SP E C TR A
TH E
OF
E LEME N TS
49
ON
50
THE
SE R I ES S PE C TRA OF T HE E L EME N T S
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
.
51
AP
277
2
7
( )
multiple
of
gr
our
n otatio n
8
2
( )
ON T HE SE R I ES S P E C T RA OF T HE E L EME N T S
52
ON
T HE SE R I ES S PE C TRA OF T HE E L EME N TS
53
'
ON T HE SE R I ES S P E C TRA OF T HE E L EMEN T S
54
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
55
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
58
ON
for
59
IV
C ON C L US I O N
ON T HE SE R I ES S P E C T RA OF T HE E LEME NT S
60
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
'
r ,
62
TH E
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
63
H y d r oge n
2
( )
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
( )
T HE S T RUC T UR E OF T HE A T O M AND T HE
64
n 6
2a ,,
2
,
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
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
66
( )
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
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
( )
'
T HE ST RUC T UR E
68
T HE A T O M AND T HE
or
t he
2
2
=
2p
k
27 r N 6 m
2
1
0
( )
For
27 7 N
2
47
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
70
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
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
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
72
'
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
T HE S TRUC T UR E
74
Rec e nt
or
T HE A T O M AND THE
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
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
T HE S T RUC T UR E OF T HE AT O M AND T HE
76
an d s
p ark
p e c tr a
a lc
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
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
S e r i e s d i a gr a m
a t any rate in the latter stages of the binding process where the
electron last bound comes into intimate interaction with those
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
Q
u
< k= n
( k= 2)
( lr 4)
=
(k=5)
F ig
5
:
5
.
80
P HYS I CA L
81
C o rr e s p o n d e n c e p r i n c i p l e
82
TH E
'
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
6 2
T HE S T RUC T UR E OF T HE A T O M AND T HE
84
P HY S I CA L
85
of
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
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
.
86
On
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
,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
T HE ST RUC T UR E OF T HE A TO M A N D THE
88
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
S e c o n d P e ri od
L i th i um N e o n
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
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
T HE S T RUC T UR E OF T HE A TO M AND T HE
92
PHY S I CA L
93
94
T HE
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
T HE
96
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
98
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
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
Pot a s s i u m K r y p t o n
10 1
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
,
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
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
,
103
T H E S T R U C T UR E
10 4
OF
THE
A TO M AN D T H E
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
-
105
10 6
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
10 8
Fi fth P e r i o d
Ru b i d i u m X e n o n
10 9
Ca
110
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
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
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
-
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
S u rv e y
th e p e ri od i c t a b l e
T HE S TRUC T UR E OF T HE A T O M AND T HE
114
fo u rth
1 16
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
-
O F TH E
E LEME N TS
117
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
'
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
ray s p
T HE ST RUC T UR E OF T HE AT OM AND T HE
120
121
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
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
N i t on
Fi g 5
.
sp
T HE S T RUC T UR E OF T HE AT O M AN D T HE
124
Xe non
Kryp t on
F ig
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
CONCLU S I O N
S TRUC TUR E OF T HE AT OM
T HE
126