Max Born - The Mechanics of The Atom

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THE MECHANICS OF THE ATOM
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By L. DUNOYER, Maitre de Conferences a la SorTranslated by J. H. SMITH,
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"
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be welcomed by all interested in the subject. The ground covered is

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.
will
Science Progress.
G.
BELL AND SONS, LTD., LONDON, W.C.2
THE MECHANICS OF
THE ATOM
BY
MAX BORN
PROFESSOR IN THE UNIVERSITY OF GOTTINGEN
TRANSLATED BY
J.
W. FISHER,
B.Sc.,
PH.D.
AND REVISED BY
D. R.
HARTREE,
PH.D.
LONDON
G.
BELL AND SONS, LTD.

1927
Printed in Great Britain by

& Co., LTD., EDINBURGH.
NKILL
DEDICATED IN ALL GRATEFULNESS
TO
MR HENRY GOLDMAN
OF NEW YORK
A FRIEND OF GERMAN LEARNING
WHO STANDS ALWAYS READY TO AID
PREFACE TO THE GERMAN EDITION

THE
"
title
Atomic Mechanics,"
given to these lectures which I
delivered in Gottingen during the session 1923-24, was chosen to

"
Celestial Mechanics." As the latter
correspond to the designation
term covers that branch of theoretical astronomy which deals with

the calculation of the orbits of celestial bodies according to mechanical
"
"
Atomic Mechanics is chosen to signify that the
laws, so the phrase
facts of atomic physics are to be treated here with special reference
an attempt is made, in
to the underlying mechanical principles
It may
other words, at a deductive treatment of atomic theory.
;
be argued that the theory is not yet sufficiently developed to justify

such a procedure to this I reply that the work is deliberately conceived as an attempt, an experiment, the object of which is to ascer;
tain the limits within which the present principles of atomic and
quantum theory are valid and, at the same time, to explore the ways
by which we may hope to proceed beyond these boundaries. In
order to
make
present book
"
this
programme
have called the
clear in the title, I
"
the second volume is to contain a closer

"
"
to
final
the
mechanics of the atom. I know that
approximation
the promise of such a second volume is bold, for at present we have
Vol. I
only a few hazy indications as to the departures which must be made

from the classical mechanics to explain atomic phenomena. Chief
among these indications I include Heisenberg's conception of the

laws of multiplets and the anomalous Zeeman effect
some features
of the new radiation theory of Bohr, Kramers, and Slater, such as
"
the subsequent advances of
the notion of " virtual oscillators
;
Kramers towards a quantum theory of dispersion phenomena as

well as some general considerations, which I have recently published,
;
relating to the application of the theory of perturbations to the

quantum theory. This mass of material, however, in spite of its
"
"
1
The German title
Atommechanik
corresponds to the title "Himinelsmechanik" (celestial mechanics); the title "Mechanics of the Atom" appeared,
however, preferable for this book, although, in the text, the clumsier expression
atomic mechanics has often been employed.
Vlll

i
not nearly enough for the foundation of a

The second volume may, in Consequence, remain
for many years unwritten.
In the meantime let its virtual existence serve to make clear the aim and spirit of this work.
This book is not intended for those who are taking up atomic problems for the first time, or who desire merely to obtain a survey of the
extensive range,
deductive theory.
is
theoretical problems which
it
involves.
The short
introduction, in
which the most important physical foundations of the new mechanics

are given, will be of little service to those who have not previously
studied these questions the object of this summary is not an introduction to this field of knowledge, but a statement of the empirical
results which are to serve as a logical foundation for our deductive
theory. Those who wish to obtain a knowledge of atomic physics,
without laborious consultation of original literature, should read
When they have masSommerfeld's Atombau und Spektrallinien.
;
work they
meet with no
the present
it
will
be
familiar.
The fact
a
deal
of
indeed
volume,
great
already
that many portions of this book overlap in subject-matter with
tered this
will
difficulties in
is of course unavoidable, but, even in these

a
will be discernible. In our treatment
certain
difference
portions,
to
the mechanical point of view details
is
prominence
always given
sections of Sommerfeld's
of empirical facts are given only where they are essential for the
elucidation, confirmation, or refutation of theoretical deductions.
Again, with regard to the foundations of the quantum theory, there

a difference in the relative emphasis laid on certain points this,
is
however, I leave for the reader to discover by direct comparison.

views are essentially the same as those of Bohr and his school
My
;
in
particular I share the opinion of the Copenhagen investigators, that

"
"
we are still a long way from a final quantum theory.
For the fact that it has been possible to publish these lectureq in
book form I am indebted in the first place to the co-operation of my
assistant, Dr. Friedrich Hund. Considerable portions of the text have
been prepared by him and only slightly revised by me. Many points,
which I have only briefly touched on in the lectures, have been
worked out in detail by him and expounded in the text. In this connection I must mention, in the first place, the principle of the uniqueness of the action variables which, in
of the present-day quantum theory
my opinion, constitutes the basis
the proof worked out by Hund

plays an important part in the second chapter ( 15). Further, the
account of Bohr's theory of the periodic system, given in the third
1
English translation of third edition, 1923, by H. L. Brose, Methuen
London.
&
Co., Ltd.,
PREFACE TO THE GERMAN EDITION
IX
chapter, has, for the most part, been put together by Hund. 1 also
wish to thank oth$r collaborators and helpers. Dr. W. Heisenberg
has constantly helped us with his advice and has himself contributed
certain sections (as, for example, the last on the helium atom)
Dr.
;
Nordheim has assisted in the presentation of the theory of perturbations, and Dr. H. Kornfeld has verified numerous calculations.
L.
MAX
G6TTINGEN, November 1924.
BORN.
AUTHOR'S PREFACE TO THE

ENGLISH EDITION
of this book in German, the mechanics
atom has developed with a vehemence that could scarcely
be foreseen. The new type of theory which I was looking for as
SINCE the original appearance

of the
the subject-matter of the projected second volume has already

appeared in the new quantum mechanics, which has been developed
from two quite different points of view. I refer on the one hand
quantum mechanics which was initiated by Heisenberg, and

developed by him in collaboration with Jordan and myself in Germany, and by Dirac in England, and on the other hand to the wave
to the
mechanics suggested by de Broglie, and brilliantly worked out by

Schrodinger. There are not two different theories, but simply two
modes of exposition. Many of the theoretical difficulties

discussed in this book are solved by the new theory. Some may
different
be found to ask
if,
English translation
me
that the time
be built up on
classical theory.
is
its
in these circumstances, the appearance of an

I believe that it is, for it seems to
justified.
is
not yet arrived
when
the
new mechanics can
own
It
foundations, without any connection with

would be giving a wrong view of the historical
development, and doing injustice to the genius of Niels Bohr, to

represent matters as if the latest ideas were inherent in the nature
and to ignore the struggle for clear conceptions

which has been going on for twenty-five years. Further, I can
state with a certain satisfaction that there is practically nothing in
of the problem,
the book which I wish to withdraw.
The
difficulties are
always
openly acknowledged, and the applications of the theory to empirical
details are so carefully formulated that no objections can l)e made
from the point of view of the newest theory. Lastly, I believe that
this book itself has contributed in some small measure to the
promotion of the new theories, particularly those parts which have
been worked out here in Gottingen. The discussions with my
collaborators Heisenberg, Jordan and Hund which attended the
Xii
writing of this book have prepared the way

which we owe to Heisenberg.
for the critical step

*
therefore, with a clear conscience that I authorise the English

translation. It does not seem superfluous to remark that this book
It
is
is,
not elementary, but supposes the reader to have some knowledge
of the experimental facts and their explanation. There exist excellent books from which such knowledge can easily be acquired. In
Germany Sommerfeld's Atombau und SpeJctrallinien is much used

an English translation has appeared under the title Atomic Structure
and Spectral Lines. I should like also to direct attention to Andrade's
book, The Structure of the Atom, in which not only the theories but
also the experimental methods are explained.
I desire to offer my warmest thanks to Professor Andrade for
suggesting an English edition of my book. I also owe my thanks
:
who prepared the translation in the first place

Professor Andrade, Professor Appleton and Dr. Curtis, who read it
over and finally to Dr. Hartree, who revised the translation, read
to Mr. Fisher,
the proof-sheets, and

certain points.
made many
I also offer
my
helpful suggestions for elucidating

sincere thanks to the publishers for
the excellent manner in which they have produced the book.
MAX BORN.
GETTING EN, January
1927.
NOTE
chief departures from the German text which have been made
Professor Born or with his approval are (1) some modifications in
THE
by
1,2 concerning the mechanism of radiation, in view of the experiments of Geiger and Bothe, and of Compton and Simon, (2) a modification of the derivation, on the lines suggested by Bohr, of the
Rydberg-Ritz series formula in 26, and (3) various alterations in
24 and 30-32, made in view of the development of ideas and the
additional experimental data acquired since the German edition was
written.
D. R. H.
CONTENTS
INTRODUCTION
PHYSICAL FOUNDATIONS
PAGE
&
1.
2.
3.
DEVELOPMENT OF THE QUANTUM THEORY OF AN OSCILLATOR

FROM THE THEORY or RADIATION
GENERAL CONCEPTION OF THE QUANTUM THEORY
THE CONCEPTIONS OF ATOMIC AND MOLECULAR STRUCTURE
...
6
12
FIRST CHAPTER
THE THEORY OF HAMILTON AND JACOBI
4.
5.
6.
7.
8.
EQUATIONS OF MOTION AND HAMILTON'S PRINCIPLE.

THE CANONICAL EQUATIONS
CYCLIC VARIABLES
CANONICAL TRANSFORMATIONS
THE HAMILTON- JACOBI DIFFERENTIAL EQUATION
17
20
24
28
36
SECOND CHAPTER
PERIODIC AND MULTIPLY PERIODIC MOTIONS
PERIODIC MOTIONS WITH ONE DEGREE OF FREEDOM

THE ADIABATIC INVARIANCE OF THE ACTION VARIABLES AND THE
QUANTUM CONDITIONS FOR ONE DEGREE OF FREEDOM
llf THE CORRESPONDENCE PRINCIPLE FOR ONE DEGREE OF FREEDOM
12. APPLICATION TO ROTATOR AND NON-HARMONIC OSCILL YTOR
13. MULTIPLY PERIODIC FUNCTIONS
14. SEPARABLE MULTIPLY PERIODIC SYSTEMS
15. GENERAL MULTIPLY PERIODIC SYSTEMS.
UNIQUENESS OF THE
ACTION VARIABLES
16. THE ADIABATIC INVARIANCE OF THE ACTION VARIABLES AND THE
QUANTUM CONDITIONS FOR SEVERAL DEGREES OF FREEDOM
17. THE CORRESPONDENCE PRINCIPLE FOR SEVERAL DEGREES -OF
9.
45
52
10.
....
18.
19.
20.
FREEDOM
METHOD OF SECULAR PERTURBATIONS
QUANTUM THEORY OF THE TOP AND APPLICATION TO MOLECULAR
MODELS
COUPLING OF ROTATION AND OSCILLATION IN THE CASE OF
DIATOMIC MOLECULES
60
63
71
76
86
95
99
107
110
122
XVI
THIRD CHAPTER
r
SYSTEMS WITH ONE RADIATING ELECTRON

PA.GB
21.
22.
23.
24.
MOTIONS IN A CENTRAL FIELD OF FORCE

.130
THE KEPLER MOTION
139
SPECTRA OP THE HYDROGEN TYPE
147
THE SERIES ARRANGEMENT OP LINES IN SPECTRA NOT OF THE
.
HYDROGEN TYPE
161
....
25.
ESTIMATES OF THE ENERGY VALUES OF THE OUTER ORBITS IN

SPECTRA NOT OF THE HYDROGEN TYPE
26.
THE RYDBERG-RITZ FORMULA

THE RYDBERG CORRECTIONS FOR THE OUTER ORBITS AND THE
27.
155
161
POLARISATION OF THE ATOMIC CORE
165
37.
THE PENETRATING ORBITS

169
THE X-RAY SPECTRA
173
ATOMIC STRUCTURE AND CHEMICAL PROPERTIES
.180
THE ACTUAL QUANTUM NUMBERS OF THE OPTICAL TERMS
183
THE BUILDING UP OF THE PERIODIC SYSTEM OF THE ELEMENTS
191
THE RELATIVISTIC KEPLER MOTION
201
THE ZEEMAN EFFECT
207
THE STARK EFFECT FOR THE HYDROGEN ATOM
.212
THE INTENSITIES OF LINES IN THE STARK EFFECT OF HYDROGEN
220
THE SECULAR MOTIONS OF THE HYDROGEN ATOM IN AN ELECTRIC
38.
THE MOTION OF THE HYDROGEN ATOM
39.
THE PROBLEM OF Two CENTRES
28.
29.
30.
31.
32.
33.
34.
35.
36.
FIELD
229
IN CROSSED ELECTRIC
AND
MAGNETIC FIELDS
235
241
FOURTH CHAPTER
THEORY OF PERTURBATION
40.
THE SIGNIFICANCE OF THE THEORY OF PERTURBATIONS FOR THE

MECHANICS OF THE ATOM
41.
PERTURBATIONS OF A NON-DEGENERATE SYSTEM

APPLICATION TO THE NON-HARMONIC OSCILLATOR
PERTURBATIONS OF AN INTRINSICALLY DEGENERATE SYSTEM
AN EXAMPLE OF ACCIDENTAL DEGENERATION
PHASE RELATIONS IN THE CASE OF BOHR ATOMS AND MOLECULES
42.
43.
44.
45.
46.
47.
48.
49.
I.
....
....
.
LIMITING DEGENERATION
PHASE RELATIONS TO ANY DEGREE OP APPROXIMATION
THE NORMAL STATE OF THE HELIUM ATOM
THE EXCITED HELIUM ATOM
APPENDIX
II.
Two THEOREMS
IN THE THEORY OP NUMBERS

ELEMENTARY AND COMPLEX INTEGRATION
INDEX
....
247
249
257
261
265
269
275
282
286
292
300
303
313
THE MECHANICS OF
THE ATOM
INTRODUCTION
1.
Development of the Quantum Theory of the

from the Theory of Radiation
Oscillator
BEFORE dealing with the mathematical theory of atomic mechanics

we shall give a brief account of its physical foundations. There are
two sources to be considered on the one hand the theory of thermal
on the
radiation, which led to the discovery of the quantum laws
of
atoms
and
structure
the
of
molecules.
other, investigations
Among all the characteristics of the atom which can be inferred
from the physical and chemical properties of bodies, the radiation
:
phenomena are distinguished by the fact that they provide us with

the most direct information regarding the laws and structure of the
ultimate constituents of matter. The most universal laws of matter
are those manifested in such
phenomena as are independent of the

nature of the particular substance with which we are dealing. This
constitutes the importance of KirchhoiFs discovery that the thermal
is independent of the nature of the material
or contained in its interior. In an
the
walls
of
the
enclosure,
forming
enclosure uniformly filled with radiation in equilibrium with the
radiation in an enclosure
surroundings, the energy density, for a range of frequency dv, is

equal to pjdv, where p v is a universal function of v and the temperature T.
From
homogeneous
the standpoint of the wave theory the macroscopic

is to be regarded as a mixture of waves of
radiation
every possible direction, intensity, frequency, and phase, which is

in statistical equilibrium with the particles existing in matter which
emit or absorb
light.
For the theoretical treatment of the mutual interaction between

radiation and matter it is permissible, by Kirchhoff s principle, to replace the actual atoms of the substances by simple models, so long
as these do not contradict any of the known laws of nature. The
1
has been used as the simplest model of an atom

the moving partible is considered to be
an electron, which is bound by the action of quasi-elastic forces to a
position of equilibrium at which a positive charge of equal magnitude
harmonic
oscillator
emitting or absorbing light
We
thus have a doublet, whose moment (charge X

with time. H. Hertz showed, when investigatvaries
displacement)
of
electric waves, how the radiation from such a
the
ing
propagation
is
situated.
may be calculated on the basis of Maxwell's equations. It

an even simpler matter to calculate the excitation of such an
oscillator by an external electromagnetic wave, a process which is
utilised to explain refraction and absorption in the classical theory of
dispersion. On the basis of these two results the mutual interaction
between such resonators and a field of radiation may be determined.
M. Planck has carried out the statistical calculation of this interdoublet
is
He found that the mean
action.
energy
W of a system of resonators
proportional to the mean density of radiation p v

the proportionality factor depending on v but not on the temof frequency v
perature
is
The complete determination of p v (T) is thus reduced to the determinamean energy of the resonators, and this can be found from
tion of the
the laws of the ordinary statistical mechanics.

Let q be the displacement of a linear oscillator and %q the restoring
then p=mij is the momentum, and the
force for this displacement
;
energy
The
is
force-coefficient
the true frequency v
x is connected with the angular frequency

I
by the relation
^ ==a) 2 =
m
According to the rules of
statistical
2 7rv) 2
u and
mechanics, in order to calculate
of a quantity depending on p and q the quantity

must be multiplied by the weighting factor e-*w where /J=1/T, and
"
"
then averaged over the whole of the
(p, q) correphase space
the
mean value
sponding to possible motions.
Thus the mean energy becomes
1
In the following co will always be used to denote the number of oscillations or
rotations of a system in 2n sees, (the angular frequency), v will be used to denote the
number in 1 sec. (the true frequency).
This can clearly also be written
W^logZ,
where
is
the so-called partition function (Zustandsintegral).
tion of
The evalua-
gives
- f*
J
s'
-*
f*
cM
tt>
*'dgi
-f>
and since
we
get
Hence
W
W_
(%}
(2)
r-TM.
This leads to the following formula for the density of radiation

_
/q\
(3)
T,rv\
t
jf"^
'
the so-called Rayleigh-Jeans formula. It is at variance not only with

the simple empirical fact that the intensity does not increase continually with the frequency, but also leads to the impossible consequence that the total density of radiation
is infinite.
The formula (3) is valid only in the limiting case of small v (long
waves). W. Wien put forward a formula which represents correctly
the observed decrease in intensity for high frequencies. A forriiula
which includes both of these others as limiting cases was found by
Planck, first by an ingenious interpolation, and shortly afterwards
derived theoretically. It is
87T1/
where A
is
llV
a new constant, the so-called Planck's Constant. Since
4
it is
the fundamental constant of the whole
numerical value
will
quantum
be given without delay, viz.
theory,
its
h =6-54. 10-27 erg sec.

with (1) shows that this radiation formula corre-
Comparison of (4)
sponds to the following expression
for the energy of the resonators
W=^-.
(5)
To
derive this formula theoretically, a complete departure from

the principles of classical mechanics is necessary. Planck discovered
that the following assumption led to the required result

the energy
of an oscillator can take not all values, but only those which are multiples
:
of a unit of energy
According to this hypothesis of Planck, the integral formula for
is to be replaced by the sum
.
oo
The summation
of this geometric series gives

*
7
L
1
From
__f/W
Z=2*
n=0
(6)
this it follows that
thus
W=-^L.1
(7)
6*T
This agrees with Planck's formula
(5) if
we put Vf =hv. This
last
relation can be established with the help of Wien's displacement law,
which can be deduced from thermo-dynamical considerations combined with the Doppler principle. Wien's law states that the density
of radiation must depend on the temperature and frequency in the
following
way
the energy of the resonator has therefore the form
W-rffg).
Comparison with
(7)
shows that
must be proportional
to
v.
Einstein showed that the behaviour of the specific heat of solid

bodies furnished valuable support for Planck's bold hypothesis of
atoms
energy quanta. The crudest model of a solid consisting of
a system of 3N linear oscillators, each of which more or less represents the vibration of an atom in one of the three directions of space.
is
If
the energy content of such a system be calculated on the assump-
we
tion of a continuous energy distribution,
we
get
from
(2)
consider one
gram molecule, then NA;=K, the absolute gas

we
and
have
the law of Dulong and Petit in the form
constant,
If
cv
dK
--=3R=5-9
calories per degree C.
rfj_
Experiment shows, however, that this is the case at high temperatures only, while, for low temperatures, c v tends to zero. Einstein
took Planck's value (5) for the mean energy instead of the classical
one and obtained for one gram molecule
:
fo
JfeT
E=31lT- r
hv
ekr
This represents, with fair accuracy, the decrease in c v at low temperatures for monatomic substances (e.g. diamond). The further
development of the theory, taking into account the coupling of the

atoms with one another, has confirmed Einstein's fundamental
hypothesis.
Whereas Planck's assumption of energy quanta
for resonators is
by this result, a serious objection may be brought

of his radiation formula, namely, that the rededuction
his
against
well substantiated
lation (1) between the density of radiation p v and the mean energy
of the resonators is derived from classical mechanics and electro-
is based on the
dynamics, whereas the statistical calculation of
which
cannot
be
reconciled
with
classical conquantum principle,
siderations. Planck has endeavoured to remove this contradiction
by the introduction of modified quantum restrictions but further

developments have shown that the classical theory is inadequate to
explain numerous phenomena, and plays rather the role of a limiting
;
case (see below), whereas the real laws of the atomic world are pure
quantum laws.
s/Let us recapitulate clearly the points in which the quantum
principles are absolutely irreconcilable with the classical theory.
According to the classical theory, when a resonator oscillates, it

emits an electromagnetic wave, which carries a Way energy in consequence the energy of the oscillation steadily decreases. But according
;
quantum theory, the energy of the resonator remains constant

during the oscillation and equal to n Uv a change in the energy of the
resonator can occur only as the result of a process in which n changes
to the
"
by a whole number, a quantum jump."
A radically new connection between radiation and the oscillation
of the resonator must therefore be devised. This may be accomplished in two ways. We may either assume that the resonator does
not radiate at all during the oscillation, and that it gives out radiation of frequency v only when a quantum jump takes place, there
being some yet unexplained process by which energy lost or gained by
the resonator is given to or taken away from the ether. The energy
principle is then satisfied in each elementary process. Or we may
assume that the resonator radiates during the
oscillation,
but retains
energy in spite of this. The energy principle is then no longer

obeyed by the individual processes it can only be maintained on an
its
average provided that a suitable relation exists between the radiation and the probabilities of transitions between the states of constant
energy.
The
conception was long the prevailing one the second

1
was
hypothesis
put forward by Bohr, Kramers, and Slater, but new
2
3
experiments by Bothe and Geiger, and by Compton and Simon,
have provided strong evidence against it. The investigations of this
book will, in general, be independent of a decision in favour of either
of these two assumptions. The existence of states of motion with
first
constant energy (Bohr's
"
stationary states ") is the root of the

are
we
concerned in the following pages.
with
which
problems
2.
General Conception ot the
By consideration
of Planck's formula
Quantum Theory
=hv, Einstein was led to
interpret phenomena of another type in terms of the quantum theory,

thus giving rise to a new conception of this equation which has proved
very
fruitful.
effect.
The phenomenon
If light of
are set free
and
in question is the photoelectric

on a metallic surface, 4 electrons
frequency v falls
it is
found that the intensity of the light influences
Zeitschr. f. Physik, vol. xxiv, p. 69,
W. Bothe and H. Geiger, Zeitschr. f. Physik, vol. xxxii, p. 639, 1925.

A. H. Compton and W. Simon, Phys. Rev., vol. xxv, p. 306, 1925.
1924; Phil. Mag., vol.
xlvii, p. 785, 1924.
4
When the symbols v and v are employed concurrently, v always refers to the
frequency of the radiation, the symbol r to a frequency within the atom. (Trans-
lator's note.)
the number of electrons emitted but not their velocity. The latter
depends entirely or- the frequency of the incident light. Einstein
suggested that the velocity v of the emitted electrons should be given
by the formula
which has been verified for high frequencies (X-rays), while for low
frequencies the work done in escaping from the surface must be taken
into consideration.
We have then
an
electron, loosely
bound
in the metal, ejected
by
the incident light of frequency v and receiving the kinetic energy hv

the atomic process is thus entirely different from that in the case of
;
the resonator, and does not contain a frequency at all. The essential
point appears to be, that the alteration in the energy of an atomic
system is connected with the frequency of a light-wave by the
equation
(1)
*P=W 1 -W
fc
no matter whether the atomic system possesses the same frequency

v or some other frequency, or indeed has any frequency at all.
Planck's equation
W=n.W W
;
=Ai/
gives a relation between the frequency of oscillation v of a resonator

its energy in the stationary states, the Einstein equation (1)
and
gives a relation between the change in the energy of an atomic

system for a transition from one state to another and the frequency
v of the monochromatic light with the emission or absorption of
which the transition is connected.
Whereas Einstein applied this relation solely to the case of the
liberation of electrons
by incident
light
and to the converse
process,
the production of light (or rather X-rays) by electronic bombardment, Bohr recognised the general significance of this quantum
viz.
principle for all processes in which systems with stationary states

interact with radiation. In fact the meaning of the equation is in-
dependent of any special assumptions regarding the atomic system.

Since Bohr demonstrated its great fertility in connection with the
hydrogen atom, equation (1) has been called Bohr's Frequency
condition.
Taking into account the new experiments by Bothe and Geiger,

and by Compton and Simon, which have been mentioned above,
we have to assume that the frequency v is radiated during the
transition and the waves carry with them precisely the energy hv
quantum) there is at present no theoretical indication of

the detailed nature of the transition process. *
If Bohr's frequency relation (1) be applied to the resonator we are
(light
faced by alternatives which will now be considered.

The change of
takes
which
the
when
resonator
the state
from
place
energy
passes
with the energy njiv to that with the energy n 2kv,
viz.
in general, a multiple of the energy quantum, hv, of the resonator.

According now to Bohr and Einstein, this change in energy must be
connected with the frequency ? of the emitted monochromatic radiais,
tion
by the equation
hv=(n 1
n 2 )hv.
This admits of two possibilities only either we may require that, as

in the classical theory, the radiated frequency shall correspond with
:
that of the radiator, in which case only transitions between neigh-
bouring states, for which

i
are possible, or
differs
w a =l
we may assume that the frequency
from that
of the resonator, being a multiple of
of the radiation
it.
In the latter
case the emitted light will not be monochromatic, on account of the

possibility of different transitions. The decision between these two
possibilities
ment
has been attained in the course of the further develop-
of Bohr's atomic theory, the conclusion being that the emitted
monochromatic, with the frequency given by the

but
that
the agreement between the frequency of the
(1),
radiation and the frequency of oscillation of the resonator (i.e.
radiation
is strictly
condition
nl
n 2 =l) is brought about by an additional principle, which provides a criterion for the occurrence of transitions between the
and is called the Correspondence Principle.

fundamental difference between the quantum theory and the
classical theory is that, in the present stage of our knowledge of the
"
"
elementary processes, we cannot assign a cause for the individual
quantum jumps. In the classical theory, the transition from one
state to another occurs causally, in accordance with the differential
equations of mechanics or electrodynamics. The only connection in
which probability considerations find a place on the older theory is in
different states,
the determination of the probable properties of systems of many

degrees of freedom (e.g. distribution laws in the kinetic theory of
In the quantum theory, the differential equations for the
gases).
transitions
between stationary states are given up, so that in this

must be sought. These transitions are analogous
case special rules
to the processes of radioactive disintegration. All experiments go

to show that the radioactive transformation processes occur spon-
taneously and are not capable of being influenced in any way.

They appear to obey only statistical laws. It is not possible to
say when a given radioactive atom will disintegrate, but it is possay what percentage of a given number will disintegrate in
a given period
or, what comes to the same thing, a probability
can be assigned for each radioactive transformation (which is
sible to
called a priori since we are not at present in a position to express

in terms of anything more fundamental).
transfer this
We
it
conception to the states of an atomic system. We ascribe to each

transition between two stationary states an a priori probability.
The theoretical determination of this a priori probability is one of

the most fundamental problems of the quantum theory. The only
method of attack so far available is to consider processes in which the
energy transformed in the course of a single transition is small in comparison to the total energy, in which case the results of the quantum
theory must tend to agree with those of the classical theory. One
theorem based on this idea is the Correspondence Principle of Bohr
mentioned above here the transitions between states with large
quantum numbers (e.g. for large n in the case of a resonator) are
compared with the corresponding classical processes. The rigorous
;
formulation of this principle will be given later.

Another application of this idea occurs in a
Planck's radiation formula
this is
effective support to the ideas of the
new
derivation of
due to Einstein, and has given
quantum theory and in particular
to Bohr's frequency condition.

In this case no assumptions are
made regarding the radiating sysdifferent

possesses
stationary states of constant
these we select two with the energies
x and
2
tem except that
From
energy.
(W 1 >W 2
atoms
),
it
and suppose
in these states are
respectively.
that,
when
statistical equilibrium exists,
present in the numbers
and
Then, by Boltzmann's Theorem
N 2 -<r*r
1
w -w.
t
-.
*T
e kT
According to the classical theory, the mutual interaction between an

atomic system and radiation consists of three kinds of processes
:
If
the system exists in a state of higher energy,
it
radiates energy
spontaneously.
2.
The
field of radiation gives
up energy to or takes away energy
10
from the system according to the phases and amplitudes of the waves
of which it is composed. We call these processes
(a) positive in-radiation,
if
the system absorbs energy
negative in-radiation (out-radiation), if it gives up energy.

In the cases 2 (a) and 2 (6) the contributions of the processes to the
(6)
alteration of the energy are proportional to the energy density of the

radiation.
In an analogous manner we assume for the quantum interaction

between radiation and atomic systems the three corresponding processes. Between the two energy levels
x and
2 there are then the
following transitions
1. Spontaneous decrease in energy
:
2
l to
by transition from
The frequency with which this process occurs is proportional to the
number N x of the systems at the higher level 1? but will also depend
on the lower energy state
We write for this frequency of
2
.
occurrence
2a. Increase in energy
transition
from
on account
to Wj).
of the field of radiation
(i.e.
We write in a corresponding way for its
frequency of occurrence
26.
from
Decrease in energy on account of the radiation

Wj to 2 ) with the frequency of occurrence
field (transition
We leave open the question whether the energy gained or lost by

the atomic system is subtracted from or given up to the radiation
during each individual process, or whether the energy principle is
satisfied statistically only.
Now
the statistical equilibrium of the states Nj_ and
requires
that
This gives
PV
_____
B 21
It is necessary
now
to
jj
^?
B 12 B 21e
make
12
W -W 2
*T
B 12
use of the frequency condition
a
Emstrahlung is hero translated in-radjation, as there seems to be no exact
1924) has already used in
English equivalent. E. A. Milne (Phil. Mag., xlvii, 209,
"
"
"
"
in this connection.
English the terms in-radiation and out-radiation
in order that the formula for
displacement law.
11
pv should be consistent with Wien's
Then
__
ft-
At this stage Einstein makes use of the general consideration mentioned above, that the quantum laws must reduce to the classical
ones as a limiting case. Clearly in the present problem the limiting
is that of high temperatures, where liv is small compared to AT.
In this case our formula (2) must become the Rayleigh-Jeans for-
case
mula
(3) of
experiment
1,
required by the classical theory (and verified by
for high temperatures), namely,
c3
becomes
Since, for large values of T, our p v
A 12
L~
"v
T>
tt
i
>21~ i5 12
the agreement
is
possible only
T>
>
A"
+ i>21Tm-T
,
if
B 12 =B 21
and
V
Bia
We
c*
arrive in fact at Planck's radiation formula
(3)
JL.
Collecting our results together, we see that Planck's original formulation of the quantum principles for the resonator embodies two
essentially different postulates
1. The determination of the stationary states (constant energy)
this is done in the case of the resonator by the equation
:
We shall generalise this equation later for any periodic system.

2.
The Bohr Frequency condition
Av=W 1 -W 1
which determines the frequency of the light emitted or absorbed in

the transition between two stationary states. The frequency v so
defined
is
positive for emission
and negative
for absorption.
12
In addition to this there are certain
statistical principles bearing
on the frequency of occurrence of the stationary states and of the

transitions between them, chief among which is the Correspondence
Principle already referred to.
3.
-The Conceptions of Atomic and Molecular Structure
Having now considered the development
of the special principles
underlying the quantum mechanics of the atom, we shall indicate

briefly the development of our knowledge regarding the material
substratum to which they apply.
The phenomena of electrolysis first led to the hypothesis of the

atomic structure of electricity. Subsequently the carriers of negative
electricity were detected in the free state as the cathode rays and
the j8-rays of radioactive substances. From the deviation of these
rays in electromagnetic fields, the ratio e/m, of charge to mass of
the particles, could be determined. It was found that
e/
m =5-31
10 17 E.S.U. per gram.
On
the assumption that the same elementary quantum of electricity is concerned both here and in electrolysis (which can be
verified approximately by experiment), we are led to the conclusion
that the mass of these negative particles of electricity is about an
1830th part of that of a hydrogen atom. These carriers of negative
electricity are called electrons and it can be shown, by optical and
electrical experiments, that they exist as structural units in all
matter. By making use of the fact that it is possible to produce

on very small (ultra-microscopic) metal particles, and oil drops, a
charge of only a few electrons, and to measure it, very accurate
values have been found for the charge carried by an electron.
Millikan found
e=4-77. 10- 10 E.S.U.

Positive electricity has only been found associated with masses
Positive rays have been produced and studied
of atomic magnitude.
to mention a-rays of radioactive substances, anode

canal rays. The determination of e/m from deviation ex-
it will suffice
rays and
periments gave the mass of the a-particles to be that of the

helium atom for the particles of the anode rays the mass is that
of the atom of the anode material, while for the particles of the
canal rays the mass is that of an atom of the gas in the tube. We
;
must therefore assume that each atom consists of a positive particle,

at which is concentrated most of its mass, and of a number of
electrons.
In the neutral atom the number of the elementary
charges of the positive particle
positive ions result
of extra electrons.
from
is
13
equal to the number of electrons
loss of electrons, negative ions
from capture
As regards the size of the electrons we can do nothing but make

doubtful theoretical deductions, which lead to an order of magnitude
of 10~ 18 cm.
Lenard was the
first
to obtain definite conclusions
regarding the size of the positive particles, which he called dynamids

(Dynamiden). From experiments on the penetration of matter by
cathode rays, he found that only a vanishingly small fraction of the
space occupied by matter is impenetrable to fast cathode rays.
Subsequently Eutherford arrived at analogous conclusions, as the
result of experiments on the penetration of matter by a-rays. From
a study of the range and scattering of these rays he was able to
establish the fact that the linear dimensions of the positive particles,
which he named nuclei, are at least 10,000 times smaller than those
an atom up to this limit the observed deviations can be ascribed

Coulomb forces between the charged particles. The measurements also provided information regarding the charge of the positive
particles, and gave for the number of the elementary charges about
of
to
the number of electrons in the

half the value of the atomic weight
neutral atom must be the same. This result was supported by
;
the amount of the scatinvestigations of the scattering of X-rays

at
in
rate
the
case of loosely bound
tering depends principally,
any
;
electrons,
on their number only.
When we come
to regard all the possible types of atoms we must

turn for guidance to the periodic system, which has been set up as
the result of chemical experience.
By this, the elements are
arranged in an absolutely definite order the magnitudes of the

atomic weights give in the main the same order, but there are
The result obcertain discrepancies (e.g. argon and potassium).
;
tained above, that the nuclear charge is approximately equal to

half the atomic weight, led van den Broek to the hypothesis that the
number
number
of elementary nuclear charges is the same as the ordinal

of the atom in the periodic system (atomic number or
When, following Laue's discovery, X-ray spectrobeen

had
begun by Bragg, van den Broek's hypothesis
scopy
was confirmed by Moseley's investigations on the characteristic
X-ray spectra of the elements. Moseley found that all elements
possess essentially the same type of X-ray spectrum, but that with
increasing atomic number the lines are displaced in the direction of
order number).
higher frequencies and, moreover, that the square root of the frequency always increases by nearly the same amount from one
14
element to the next. This established the fundamental character

of the atomic number, as contrasted with the atomic weight.
Further, the similarities of the X-ray spectra suggest the similarity
If now we assume that
of certain features of atomic structure.
i.e. number and arrangement of its
determined essentially by the nuclear charge, we are
led to the conclusion that there must be a close relationship between the nuclear charge and the atomic number in fact, with
the structure of the atom,

electrons, is
the assumption that the two quantities are equal, the more precise
theory of the X-ray spectra, which we shall give later, leads to
Moseley's law.
Collecting together the results bearing on atomic structure, we have
then the following picture of an atom with the order number Z it
consists of a nucleus with the charge Z, 1 with which is associated
practically the whole mass of the atom, and (in the neutral state)
;
In the model
electrons.
atom imagined by Rutherford
it is
supposed that these circulate round the nucleus in much the same
way as the planets round the sun, and that the forces holding them
together are essentially the electrostatic attractions and repulsions
of the charged particles.
But if, on the basis of these conceptions and the classical principles, we now attempt to develop a mechanical theory of the atom,
we encounter the
a system of
following fundamental difficulty
such
as
is
in
this
model, would
moving
pictured
to
radiation
and must
lose
electromagnetic
energy owing
continually
therefore gradually collapse. Further, all efforts to deduce the char:
electric charges,
acteristic structure of the series spectra
on the basis of the
laws have proved fruitless.

Bohr has succeeded in overcoming these
difficulties
classical
by rejecting the
favour of the quantum principles discussed in

postulates the existence of discrete stationary states,
classical principles in
1
and
2.
He
by quantum conditions, the exchange of energy between these

and the radiation field being governed by his frequency con2
dition ( 1 )
The existence of a stationary state of minimum energy,
which the atom cannot spontaneously abandon, provides for the
absolute stability of atoms which is required by experience. Further,
fixed
states
Later researches, chiefly by J. J. Thomson, Rutherford, Aston, and Dempster,

have shown that the nucleus itself is further built up of electrons and hydrogen
As a consequence of these investigations the old hypothesis
nuclei, called protons.
of Prout regains significance, in a somewhat different form.
The deviations of
the atomic weights from whole-number values, which previously ruled out this
hypothesis, can be accounted for by the conception of isotopes and energy-mass
Not much is definitely known on the subject of nuclear mechanics,
variations.
and it will not be discussed in this book.
15
hydrogen atom, he succeeded in calculating the

a
rational generalisation of Planck's hypothesis,
by
energy
in such a way that the frequency condition leads at once to the ob-
in the case of the

levels
served spectrum (Balmer's formula), He has also given the principles whereby the quantum conditions may be formulated in
more complicated
cases
this will be dealt with in the following
pages.
Bohr's fundamental concepts of discrete stationary states and a

quantum frequency condition receive their most direct confirmation
from a
class of investigations initiated
by Franck and Hertz, and sub-
sequently extended and refined by these and other investigators.

The fundamental idea of these experiments is that definite amounts
of energy can be communicated to atoms by bombarding them with
electrons of
is
known
velocity.
As the
velocity of the
bombarding
increased, the abrupt occurrence of the stationary states

indicated on the one hand by the sudden appearance of electrons
electrons
is
which have lost some of their incident energy, and on the other by
the sudden production of radiation of those frequencies which are
associated with transitions from the stationary state in question to
other stationary states of lower energy.
Analogous phenomena are observed in the domain of the X-rays,
where the occurrence of emission lines and absorption edges is bound
up with the attainment of definite energy levels, consequent on

bombardment. In both the optical and the X-ray region
values for the constant h can be determined by means of the frequency
condition by measuring the energy supplied and the frequency of the
consequent radiation. These values are independent of the atom and
the particular quantum transition used to derive them, and are found
electronic
to be in good agreement with the values obtained from heat radiation
measurements.
Not only the structure of atoms but also their combination to form
molecules and extended bodies, and the laws of motion of the latter,
are governed by the same quantum laws. We may mention, for
example, the more precise development of the theory of specific heats
of solid bodies already referred to, and further the theory of the band
spectra of molecules, which
we
shall deal
with in detail in this
book.
We
give in conclusion a brief formulation of the ideas which have

led to Bohr's atomic theory. There are two observations which are
fundamental firstly the stability of atoms, secondly the validity of
:
the classical mechanics and electrodynamics for macroscopic processes. The application of the classical theory to atomic processes
16
leads,

however, to
difficulties in
connection with the stability.
The
problem arises, therefore, of developing a mechanics of the atom free

from these contradictions. This new mechanics is characterised by
the fact that the classical continuous manifold of states
by a discrete manifold, defined by quantum numbers.
is
replaced
FIRST CHAPTER
4.
Equations of Motion and Hamilton's Principle
NEWTON'S equations
of
starting-point for
the following considerations
all
motion
for a
where
system of
free particles
form the
l
:
__
m k denotes the mass of the Ath particle, v its velocity, and K k

The product m v is called the impulse or
fc
the force acting on
it.
fc
fr
momentum.
In this form the equations (1) still hold if the mass is dependent
on the magnitude of the velocity, as is required by Einstein's rela*
tivity theory.
In many cases the system of equations (1) is equivalent to a variation principle, known as Hamilton's Principle, viz.
:
(2)
Here
ig
Ldt =stationary value.
a certain function of the co-ordinates and velocities of
all
the particles, and, in certain circumstances, also an explicit function

of the time, and equation
as an expression of Hamilton's Principle
(2)
to be interpreted as follows the configuration (co-ordinates) of the
system of particles is given at the times t t and t 2 and the motion is
is
sought (i.e. the co-ordinates as function of the time) which will take
the system from the first configuration to the second in such a way
that the integral will have a stationary value. 2 The chief advantage
of such a variation principle is its independence of the system of coordinates.
1
Vector products are indicated

or by absence of brackets.
or a minimum or a saddle-point
Heavy type is used to indicate vector quantities.
by square brackets, and scalar products by round brackets
9
It does not matter whether it
value.
is
maximum
17
18
Lagrange's equations
d
(3)
SL_aL
dtdFT'fa
1
can be derived directly from the variation principle (2). We have

to determine L so that these equations agree with the Newtonian
equations (1).
If the forces
K* have
we determine a
a potential U,
function
T*
i.e. if
of the velocity
components so that
0T*
The equations
(1)
can then be written in the form
0T*_8(-U)_
dx k
dt dJr k
or
rfd(T*-U)_d(T*-U)_
rf/T
We put therefore in our variation principle

L=T*-U.
(4)
If,
'
dx~k
d7^
(2)
k as
taking no account of the theory of relativity, we regard
T* is equal to the kinetic energy T. If we write, in accord-
constant,
ance with the special theory of relativity,

'
c/J
"
where m is the
(for one particle)
rest
mass
"
and
c is
the velocity of light,

1
(5)
T*=m - eri-(l-(-)
which, for the limiting case c
oo
1
In the following we shall usually write
corresponding to the co-ordinates x, y t z.
c
\ /
we have
1
!
],
reduces to the expression
down only the first
v2
of the three equations
19
This function differs from the kinetic energy

2
T=m
(6)
c({l-(*) j~ -l],
which, of course, also reduces to
c=oo
^m
v 2 in the limiting case where
Besides a component K, which can be derived from a potential

U, the forces often contain a component K* depending on the
velocities (as in the case of
function
magnetic forces acting on electric charges).
M is then determined so that
-*
and the expression
L=T*-U-M
(8)
substituted in the variation principle
is
(2).
The Lagrangian equations (3) then become

d 8M. 0M_
d #T* dU
and our variation principle
equations of motion
is,
in fact, equivalent to the
is also valid when the

manner defined by equations
*
0=0
/*(*!> 2/i> *i *>
Hamilton's Principle
strained in a
Newtonian
particles are con-
between the co-ordinates. 1
In accordance with the rules of the
calculus of variations, additional forces of the
must be added to the
form
where the A^'s, which are

"
undetermined multipliers
of Lagrange. These multipliers, together with the co-ordinates, are
the number of determining equations,
to be regarded as unknowns
i.e. differential equations and equations of constraint, is then
equal
to the number of unknowns.
As already mentioned, the chief advantage of Hamilton's Principle
is that it represents the laws of motion in a manner independent of
original forces,
functions of the co-ordinates, are the
"
any
1
special choice of co-ordinates.
If
a number of equations of con-
Such conditions, which do not involve the velocity components, are called
holonomous.
20
straint be given, an equal number of co-ordinates can be eliminated

with their help. There remains then a certain number of independent co-ordinates
qf
q^ 2
.
of degrees of freedom. The

of the j's and of their
function
will
be
a
then
function
Lagrangian
time derivatives ; the time may also appear explicitly :
The number /is known as the number
k=L(?i,
the variation principle
(2)
</!,
y2 ^ 2
,
... qr
qf
t)
then leads to the Lagrangian equations
*-"/
!!--
These are also valid if the co-ordinates q k refer to arbitrarily moving,

or even deformed, systems of reference.
5.
The Canonical Equations
Each
of Lagrange's equations is a differential equation of the

second order. In many cases, particularly for work of a general
character, it is desirable to replace them by a system of twice as
many
differential equations of the first order.
The simplest way
of accomplishing this is to put q k =s k and then to take these additional equations into account, treating the s k s, as well as the q k 's,
>
as
unknown
as follows
quantities.
A much more symmetrical form is obtained
In place of the q k 's the new variables
""
(1)
known as momenta,
4 now become
of
are introduced
p^
(2)
the Lagrangian equations
(9)
fyk
where
to be regarded as a function of the q k s and q k 's.

can now be expressed in a similar form by introducing
is still
Equations
(]
in place of the function L(7 1 r/ 1

t) a new function
l
by means of a Legendre Transformation
.
H(^ 1 ;) 1
t),
H=
(3)
1
Legendre Transformation transforms, in general, a function
function g(x,
2),
where
~*
in
f(x, y) into
such a way that the derivative of g with respect to
cy
the new variable z is equal to the old variable y
Such transformations play a
in
all
considerable part
branches of physics ; in thermodynamics, for example, the
energy and the free energy are related in the same way as two functions connected
by a Legendre Transformation.

If
now we form the
21
total differential
QT
r\T
*}T
the terms in dq k cancel out on account of (1). For the partial derivat) with respect to p k and q k we have therefore
tives of H(<npi
where the indices outside the brackets denote which variable is independent. Now with the help of the new variables we can write (2)
and (4) (which is an expression of (1)) as follows
:
dR
This
the so-called canonical form of the equations of motion.

The
t) is called the flamiltonian function.
Pi, q z p*
is
H(<7i,
>
variables q k
and p k are
said -o be canonically conjugated.
The same equations are obtained if the momenta are defined by

same way, and the function L in the variation principle (2),
(1) in the
is
i,
expressed in terms of H by means of equation (3). We have
(6)
J^?iPkQk'R(<IiPi
^L k
for the
same
cfe=stationary value,
$)
-1
possible variations as before,
i.e.
variations for which
the configurations at fixed times t L and t 2 are themselves fixed

here the q k and p k are to be regarded as the functions required. It
is easily seen that the Lagrangian equations are equivalent to (5),
;
should be noted that the derivatives of the p k & do not occur

for this reason only the values of the
explicitly in the integrand
and
it
q k s at
the times
not those of the
and
t2
can be prescribed as limiting conditions,
p k &.
All of these considerations remain valid
if the function L, and

the function H, depends explicitly on the time t. The latter
case will occur, for example, either if external influences depending
with
it
on the time are present (U depending on
t),
self-contained system, a system of reference is
or
if,
in the case of a
employed which
itself
22
performs a prescribed non-uniform motion.

involve the time explicitly, we have
If,
however,
Substituting for q k and p k from the equations of motion

that
H does not
follows
(5), it
dR n
-*-*
so that
&(PI<!I
(7)
is
first
.)
==cons ^ an^
integral of the equations of motion (5).

as to the mechanical significance of the quantity
consider first the case of the classical (non-relativistic)
We inquire now
and
mechanics.
With any
co-ordinates, in a stationary system of refer-
ence, the kinetic energy is a homogeneous quadratic function T 2 of

the velocities q k ; in moving co-ordinate systems additional linear
terms,
and terms not involving
q k> will occur, so that
we can
write
Here T n denotes a homogeneous function of the nth degree of the

which may, moreover, depend on the q k 's. By Euler's Theorem
r/fc's,
we have
thus
(8)
If
we suppose that an ordinary
potential energy
U exists,
in
which
case
L=T-U,
we have
H=T +2T -(T +T +T )+U

= -T +T +U.
1
In the case of a co-ordinate system at rest
the total energy.
H-T+U
(9)
is
(T=T 2
If
the time does not occur explicitly in H, this
gives, in conjunction with equation (7), the law of the conservation

of energy.

In the case of moving co-ordinate systems, where
may
0, it
23
T and T x are not
H is independent of the time, thus
happen that
H=const.
is
an
integral, but
not the energy integral.
Example. We consider a system of co-ordinates (|, rj) rotating with the

angular velocity (o round the axis of z. We transform to this from the stationary system (x, y) by means of the formula
x= f cos cut
% sin
\j
ry
a>t-\-
1]
sin
cut
cos
cut
z=.
The
kinetic energy then
becomes
The momenta corresponding
so that
For
we can
to the co-ordinates f
and
/?
are then
also write
H we obtain
or
If
U is symmetrical around the axis of
and
is
therefore constant.
z,
H does not contain the time explicitly
The integral
H= const.
is
It
called the Jacobian Integral.
is,
E=T+U=
which
is
however, different from the energy

(
likewise constant.
From both
integrals it follows that
E-H= const.
This gives the law of conservation of angular momentum.
If
we transform back to
x, y,
we have
H= o>Sm(^
yx).
We
have, in fact,
Z*
ATOM
THifi MJfiUJtiAJNlUS UJT THifi
We consider now the case of relativistic mechanics. By (4) and (5),

4,
we have
for a particle
L=T* U=
thus
(10)
and
=T+U,
(11)
so that in this case also
H is the total energy.
This result
dent of the co-ordinate system so long as this

6.
is
is
indepen
at rest.
Cyclic Variables
Before dealing with the general theory of the integration of the

canonical equations, we will, first of all, consider some simple cases
If the Hainiltonian function
does not contain one co-ordinate, e.g
q l9 i.e. if
H^fptfapa
it
0,
follows from the canonical equations that
?>i=0
Thus we
arrive immediately at one integral of these equations. The

co-ordinate q l is called, after Helmholtz, a cyclic co-ordinate (since il
often corresponds to a rotation about an axis).
Clearly this case always arises if the mechanical system is no1

affected by an alteration of the co-ordinate q l (e.g. by a single translation or rotation).
r n ) moves
If, for example, a system of massive particles (iir 2
under the action of mutual forces only, the potential energy will depend solely on the differences
s2
=r 2
i!,
S 8 =r 8
r1
sn
rn
rx
We
introduce as co-ordinates the components x^y^ of r x and the

is independent
Since
components 1^^ of these differences s
,
fc
of #i2/i2i,
energy
it
follows that Px p v
l
j?z
are constant.
Now
the kinetic
is
2
2/*
+^
2
)
(t=l, 2
n),
25
Since
(&=2, 3
it
n)
follows that
(*=1, 2
The three integrals

momentum.
n).
give therefore the principle of the conservation of
Another important case is that in which the potential energy remains unaltered by a rotation of the whole system about an axis fixed
in space. If l9 2
are the azimuths of the particles of the system
about this axis, we introduce as co-ordinates the magnitudes
.
(f>
<f>
others, depending only on the relative positions of the

particles with respect to one another and to the axis (for example,
cylindrical co-ordinates r k z k or polar co-ordinates r k> k ). Since the
and certain
Hamiltonian function does not depend on Oj, O a is a cyclic variable

(in this case in the true sense of the word) and the momentum p+ conjugate to
it, is
constant.
Since
(*=2, 3
n)
and
where r k
is
the distance from the axis, p^ has the value
3T
ancf
is
therefore the angular
5T
momentum about
the axis of sym-
metry.
If the massive particles move under the action of mutual forces
only, our considerations are valid for every fixed direction in space.
Since the quantity p^ is the component of the total angular momentum
in
an arbitrary direction, and is always constant, the constancy of the
momentum follows.
may happen that H depends only on the p k s,
angular
It
.)
i.e.
26
In this case the canonical equations admit of immediate integration.

We have
Here the co
fc
's
are constants characteristic of the system and a
fc ,
fi k
are
constants of integration. It will be seen from this that a mechanical

problem is solved as soon as we have found co-ordinates for which the
Hamiltonian function depends only on the canonically conjugated

momenta. The methods treated in this book will usually follow
this course. In general, such variables cannot be found by a simple
point transformation of the q k 's into new co-ordinates, but rather the
totality (qk,pk) of the co-ordinates and momenta must be transformed
to
new conjugated
We shall,
variables.
however,
1. The Rotator.
By
an axis fixed in space.
of inertia
about the
first
this
If
axis,
consider
some more examples.
we understand a rigid body which can rotate about

^ denotes the angle of rotation and A the moment
then
and the momentum corresponding to
is
<
p=Â<f>.
For motion under no forces (U~0).
H-T-1*
(1)
<f)
is
therefore cyclic,
and consequently
p= constant,
and
<=co=-,
<j>wt\-p.
A.
The motion under no

2.
forces
The Symmetrical Top.
is
therefore a uniform rotation about the axis.
If
A^ denotes
the
moment
of inertia
about an axis
axis of symmetry (z), A z the moment of inertia about the

perpendicular to the
axis of symmetry, and d^, d v , d z the components of the angular velocity in the
system of reference
(x, y, z) rigidly
fixed in the body, then
We introduce as co-ordinates the Eulerian angles 0,
<f>,
defined as follows
is the angle between the

are taken fixed in space
is the angle between the #-axis and
axis of symmetry (z) and the z-axis,
the nodal line (line of intersection between the (x, y) plane and the plane
Rectangular axes
x, y, z
<
(x, y)) 9
and
is
the angle between the a:-axis and nodal
of the angular velocity will then be
line.
The components
27
cos <-h^ sin 6 sin #,
da,=
dy=0 sin </>$ sin 6 cos ^
(2)
and the
kinetic energy
T+KAa.(0
The momenta corresponding

0T
==( A
+0
to 0,
sin 2
6)+A n (j+t cos
0)
].
are
<f>,
2
x sin
cos 2
A,
cty
In order to make the physical significance of these momenta

to replace the 0,
$ by the components of d then
clear,
we
use (2)
</>,
sin
2y=A3(da
sin
<f>
d z cos
<
<^)
sin
0+A z d 2 cos 0,
in which (d^ cos
^+ d^ sin ^) clearly denotes the angular velocity about the

nodal line and (d^sin^ dycos^) the angular velocity about a perpendicular
direction in the (#, y) plane.
We see then from the equations, that
p
p
p
is
the angular
is
the angular
the angular
is
momentum about the nodal line,

momentum about the axis of symmetry,
momentum about the direction z fixed in
space.
For motion under no forces (U=0), a simple calculation gives

J
V"*v*'
sine
this expression ^ and

consequently
In
/>
efl
V1i+
yJ 2A;
do not appear; they are therefore
constant,
p.
cyclic,
and
= constant.
we have in addition the principle of the conservation of the total angular

momentum at our disposal the integration can be completely carried out. We
Since
can take the hitherto arbitrary axis of
z in
momentum.
is
Since the nodal line
momentum about
the direction of the resultant angular

perpendicular to this, the angular
the nodal line will be
The canonical equations
give firstly
0= constant,
and then
an
28
which leads to
0H
0)(JV~*V
or
to
than
p it follows that
equal
greater
Since p.
is
essentially
cos
cos
(P+-P+
jy-fy
as can also be seen immediately.
cos
0=0,
The Hamil toman function now takes the
simple form
i/t
and
(f>
therefore execute uniform rotations with the angular velocities
8H
The motion under no
forces of the symmetrical top therefore consists of a

uniform rotation about the axis of symmetry, together with a uniform precession of this axis about the direction of the resultant angular momentum.
7.
Canonical Transformations
As already mentioned, the integration of the equations of motion

can be effected by introducing new co-ordinates having a cyclic character if such can be found. We shall therefore quite generally seek
a transformation
Pk=Pk(qi<l2
new variables again satisfy the canonical equations of

this to be the case it is necessary and sufficient that the
variation principle (6) of 5
such that the

motion.
For
fa**-
^~
p=stationary value
x^'i
shall transform into
(\
2iP*#*~"~-^(?iPi
This will be the case
if,
and only if, the
the complete derivative

variables
and of the time
and new
for, if
V be regarded as a function of the qk
or of q k p k> t, or finally of p k
canonical transformations.
,
difference of the integrands is
of a function of 2f of the old
at
;
value.
at the limits of integration will be fixed.

take
to be a function of q k q k t, or of q k p k9 1,
an.d q k , the values of
According now as we
|d=stationary
p k,
t,
we obtain four principal forms for
We
choose therefore an arbitrary function V(y 1 q^
29
t).
The
condition
is fulfilled, if
the coefficients of q k and q k and of terms independent of

,
these quantities, are the
same on both
sides, that is if
P*
(1)
=
#
H=H~
Since in general the y 's can be calculated from the equations of the
second line, and then the p k s can be calculated from the equations of
fc
as functions of the q k and p k> the system (1) replaces the

of
transformation.
equations
in
order
to obtain a canonical transformation by means of
Again,
the
first line
an arbitrary function V(g 1 p

form
r
t),
we
write our condition in the
Pi
or,
what comes to the same thing
2P*7*- H (?i>
A;
Pi
= ~2^*"H(y
1,
P!
+|v( ?1
Comparison of the
p,
coefficients of q k
and p k
gives
These equations can also be regarded as equations of transformation.
30
The third form we obtain by simply interchanging the old and new
and replacing V by
V, in order to obtain the simplest
variables,
We obtain
possible correspondence between the four forms.
?*=---
J=-
(3)
Finally, in order to arrive at the fourth form,

in the form
we write the condition
-Hfo,
t)
or
and obtain
fc^vto, ft
(4)
0,
We can express all four forms at once in the following manner In

the arbitrary function V(a? 1? x l9 x 2 x 2
t) let x k be one of the
variables q k and p k x k one of the variables q k> p k then the equations
:
av
yk=tfa*
,
dV
(5)
fc
=T s-i
ox k
give a canonical transformation. Here j/ fc is conjugated to x k and y k

to fc ; the upper sign applies to the case where the differentiation is
taken with respect to a co-ordinate and the lower one to the case of

momentum.
differentiation with respect to a
The function
31
we
shall call the generating function, or shortly, the generator, of the
canonical transformation.
Further, it must be emphasised that the canonical property of a
transformation depends in no way on the special mechanical problem if a transformation is canonical, it remains so for every form
;
of the function
shall
need
later
We now
H.
give
some transformations which we
The function
leads to the identical transformation
The function
gives, after solving (2) for
p k and
q k9 the transformation
Pl=PlP2
21=71
6)
P2=P2
q2=<J2 fqi
and the function
V =qii>i
leads to
A transformation for three
pairs of variables is provided
by
V=9&i+ViP*+9iP*+9&*+9&*+W*
namely
Jl=Pl+P2+P3
?1='/1
In
all
of these examples the co-ordinates
separate in the transformation.

condition for this is clearly, that
i,k
This function gives
(9)
*
and the momenta are kept
The
general necessary and sufficient

shall be linear in the q's and p's
:
32
If the constants
j8rf
and y are zero we have a transformation which

p k & linearly and homogeneously into the
t
transforms the q k 's and

qk
and p k
viz.
The necessary and sufficient condition that the q k
among
themselves
is
the linearity of
provides the transformation
s shall
V in the p^'s.
transform
In fact
p *~
do)
?*=/*(?! ?2
'
Linearity of V in the # 's gives, on the other hand, a transformation

of the momenta between themselves
fc
Pa
Ar
leads to
J>*=/*(pi, Pa
(11)
Tt
appears
selves, the
if
--
the variables of the one kind transform
new
among them-
variables of the second kind will be linear functions
of the old variables of the second kind, the coefficients of
be determined functions of the variables of the

free
first
which
will
kind, and the
terms arbitrary functions of the variables of the first kind.

among themselves which are
Transformations of the co-ordinates
frequently employed are those which transform rectangular coordinates into cylindrical or polar co-ordinates, and also those which
correspond to rotations of the co-ordinate system.

The function
V^^r cos </>+pyr sin <+p/

transforms rectangular co-ordinates into cylindrical co-ordinates.
It gives
(12)
x r cos
y =r sin
Z= Z
<f>
<f>
p x cos +p v sin
p xr sin +p vr cos
P;=PZ
pr
<f>
The expression
2
p* +Pt,
then becomes
<f>
<j>
=
p^
<{>
33
In transforming to spatial polar co-ordinates we take
V=pxr cos
<f>
0+p yr sin
sin
<f>
sin
Q+pf cos
6.
This function leads to the transformation
x=rcoa <sin
y=rsin ^sin
(13)
Prp x cos ^ sin 0+y,, sin ^ sin 0+2^ cos 6

p^=^pxr sin
pe =p
xr
cos
<
sin 6
cos
+jv cos
0+p
vr
sin
<
sin
sin
0p
r sin
and transforms the expression

into
2
M
P
A rotation of the rectangular co-ordinate system (x, y, z) involves

a linear transformation of the co-ordinates with constant coefficients.
The momenta transform then contravariantly. In this case, where
the coefficients a ik defining the rotation
fulfil
the conditions
<<=*)
(+*)
the contra variant transformation
The momenta
(14)
equivalent to the original one.

transform like the co-ordinates we have
is
y^==a
z
9
and
We give two further transformations, for which V depends on q k and

qk
The function
V=M*
k
gives,
by
(1),
?*=-?*
ft=ftIt therefore interchanges co-ordinates
and momenta.
A transformation frequently employed is
given
by
34
it
leads to
(15)
y=V2p cos q
and transforms the expression q*+p 2
into 2p.
The somewhat more
general function
V = ~o>j a cotg
(16)
2i
gives
*
(16')
p=V'2nia)p cos q
and transforms
mco 2
2
into
co/J.
We shall illustrate now, by means of an example, how the canonical

substitutions can be used to integrate the equations of motion.
Linear Harmonic Oscdlalor.
In this case
where q denotes the displacement,

Introducing tho
the mass, and # the elastic constant.
momentum
p=mq
and putting
m -.
we get
-S^T^
The transformation last mentioned
new variables and a and write
(16) applies then to this case.
</>
</
(18)
j>
- V 2meoa cos ^.
The Hamiltonian function then becomes
H=wa;
and the equations
of
motion give
We call the
35
a= constant
The displacement q
will therefore
be given by
sin
nuo
(cot
ft),
The canonical transformations are characterised by the fact that

they leave invariant the form of the equations of motion, or the stationary character of the integral [(6) of 5] expressing Hamilton's
This raises the question whether there are still other
principle.
invariants in the case of canonical transformations.
This
is
in fact
the case, and we shall give here a series of integral invariants introduced by PoincarS. 1
We can show that the integral

(19)
taken over an arbitrary two-dimensional manifold of the 2/-dimensional (p, q) space, is such an invariant. If we represent the twodimensional manifold by taking p k and q k as functions of two parameters u and
v,
then
~du
~du
dudv.
dv
dv
We prove the invariant character of J
by showing that
du
~dv
du
!)v
provided that p k and q k are derived from q k) p k by a canonical transformation. We write the transformation in the form (2)
av( gl
2*=
1
H. Poincar6, Mtthode* nouvelles de
(Paris, 1899)
p. 224, 1921.
la
mtcanique
clleste, vol.
proof of the invariance by E. Brody, Zeitechr.
f.
ch. xxii-xxiv
Physik, vol. vi,
iii,
36
and replace q k p k by
,
q ky
p k with the help

G
of the first equation
wpt
vq k
Hu
Hu
dv
dv
then
'
du
du
~dv
~dv
~dq kdp
-2
du
du
dp
dq k
~dv
Interchanging the indices
k,
i,
this
~dv
becomes
dp k
dq t
~du
du
&Pk
&h
dv
dv
and we now transform q k p k into q k p k by means of the second equathe integrand becomes equal to
tion of transformation
,
Z
k
du
&Pk
dv
v-v
3q,
'
<Zjfi<n,fin r
~dp
k dqi'
du
=Z
du
du
dv
dv
<W
dv
proving the invariance of the integral

The invariance of the integral
(19).
which every combination of two indices occurs in the integrand,

may be proved in a precisely similar way. The same holds true for
in
and so on. The
last integral of the series is
J/H"
Jtfp<
dpfei
dqf
The volume in the phase space is consequently invariant with respect

to a canonical transformation.
8.
The Hamilton-Jacob!
The idea underlying the method
Differential
Equation
which is so parof
atomic
mechanics
to
suited
the
(just as it is to
ticularly
problems
those of celestial mechanics) will be clear from the example of the
of integration

oscillator given in
7.
appears very awkward in this
it
Although
37
on the other hand, it is powerful enough to lead to the

end
even for some quite complicated (particularly periodic)
required
case, yet,
motions.
We
shall
now
give a general formulation for the case in
which the Hamiltonian function does not contain the time explicitly
We endeavour to transform the variables q kt p k by means of a
canonical transformation, into new variables </> k a k in such a way

that the Hamiltonian function
depends only on the quantities a
,
fc ,
which correspond to the momenta. For this purpose the most suitable form of the canonical transformations is
7. We seek there(2),
fore to determine a function
such that, by means of the transformation

a
jP*=p-S(gift
**
(1)
<*=
ca k
S(gri>?2
at, a,
C4,
aa
.)
.)
H is transformed into a function

's are then
depending only on the a k s. The
cyclic variables and
the equations of motion lead at once to the solution
<
fc
a^constant
(2)
aw
The determination
of the function
S can be made to depend on the
solution of a partial differential

equation of the
ticular case of some importance is
given
first
order.
par-
by taking W equal to 04
let
each
p k in H
OQ
be replaced by the corresponding
then S has to
a?*
satisfy the condition
/ox
(3)
This equation is
known as the Hamilton-Jacobi differential equation.
The problem is now to find a complete solution, i.e. a solution which

involves a x and
other constants of integration a 2 a3
a/,
from
the
This function S
apart
purely additive constant in S.
/I
provides a transformation
(1) of
the kind desired
at the
same time
38
the following special relations hold,

>!
= dW =1
^2=^3=
=Wf=().
C/djL
The
solution of the equations of motion will then be given

and p k if the substitutions
solution of (1) in terms of q k
by the
(4)
are made.
The problem of solving the system of 2/ ordinary differential equations of the first order, i.e. the canonical equations, is therefore equivalent to that of finding a complete solution of the partial differential
equation (3) (/being greater than 1). This is a special case of general
theorems on the relation between ordinary and partial
differential
equations.
For many purposes it is more advantageous not to single out one of

a's, as has just been done. A canonical transformation may be
carried out, in which the a 's transform into a like number of new
variables, which we shall also call 04
a/, in such a way that the
k s do not enter into the relations between the old and new a 's.
a x is transformed into
W(a 1} a 2
a,).
the
fc
fc
</)
According to a theorem proved in 7 (equation (11)), new variables

k can be introduced, which are conjugated with the a k s and are
linear functions of the old k s with coefficients depending only on the
constants a k Thus the new k s are likewise linear functions of the
(f>
(f>
</)
time and the equations of motion hold in the form (2).

The function S may be regarded as a solution of the differential
equation
depending on/ constants 04
between which and
a/,
W=WK
exists.
By
(5)
the transformation
into the function
W(a x
a^),
(1)
transforms the function
and we have here
aw
W a relation
af )
also

An important property of
39
the function S can be derived from
namely, that for a path defined
by
fixed values of the
fc
(1),
's
aS
i*
> - e
(io=
9k
is
therefore the line integral
(6)
taken along the path, where
denotes a fixed and
point of the path.

In the case of classical mechanics,
and
for a
a moving
system of co-ordinates
For in this case we
at rest, this integral has a simple significance.
have
(see (8),
5)
and thus
(7)
In the case of the theory of

2T must be replaced by
It will
relativity, if
be seen that in both cases S
creasing with the time,
it is
is
we take a
single particle,
a function continuously in-
called the Principal Function of the
system.
We will now consider the simplest

of freedom.
Then the
case,
namely, that of one degree
differential equation (5)
becomes an ordinary
one
Solving for p as a function of q and

to q, since
W, and
integrating with respect
as
y=
we
%-
find
This can also be regarded as a special case of the general formula (6).
The function S determined in this way, which contains no constants
40
apart from
motion
W,
provides the general solution of the equations of
we have
which, on solution, gives 9 as a function of the time with the conand t

stants of integration
For co-ordinate systems at rest T has the form
where //, denotes mass, moment of

We have then
so the solution for
in
inertia, or
terms of q and
some such quantity.
is
(8)
and
(9)'
-*.-
2J V/W-U(fl
V/~tf-f=.
fc
Example
Particle falling freely or projected vertically.
height of the moving body and
where g
where g
is
/LI
the mass.
The
the constant of gravitational acceleration.
is
taken equal to
W
;
it is
attained.
is
Then we have
obviously denotes the
attained, and t the instant at which

the well-known formula
Here g denotes the
potential energy
On
maximum
solving for q
height
we obtain
Example 2. The Pendulum. Here q denotes the angular displacement and

/*= A the moment of inertia of the pendulum. The potential energy, reckoned
from g=7r/2 as
zero, is
U=
Dcosg.
41
We find
p= V2A VW-hD cos q,
(10)
-j
and
if
D cos q
\/W |D- 20
sin 2
we put
2'
then
,
_U A r
2
-DJo
<*?
/
A/ sin
Sm 2
<y
sin 2 8m
The solution of this equation, which involves an elliptic integral, gives q as

a function periodic in time, and oscillatiag between -\-a and
a. For sufficiently small values of a we can write
and obtain the solution
in
We have
a simple form.
Clearly all problems for which every co-ordinate, with the exception of one, is cyclic, reduce to the case of one degree of freedom. Let
H=H(y 1 ,y 1 ,y a
.p f),
the solution will then be represented by
p 2 =a 2
pf =af
and
S=J>i
where
pt
is
(?i,
W, a 2
af )dq l9
found by solving
(11)
Therefore
,
W,
o,
o,
a/)d?1
(t=2, 3
./).
Example 3. Projectile Motion. Let gx =2 be the vertical co-ordinate,

reckoned positively upwards, and q*=x, qz y the horizontal co-ordinates, then
42
and
W=K
Since x and y are cyclic variables,
we put
2>a5=2
and obtain
p.= [2m( W- m</z) - a 2

/
~^ == f*
J,
from
""k
=
[2m(W-^)-a2 -a3 ^ ""^
2
/
being given by
It follows
2wW- a
2
2
a3 2
this that
The two other equations
of
motion follow most simply from
mx=px = a a
my=p y = a s
We find
Elimination of
the path, which
is,
from the three equations of motion gives the equations of

of course, a parabola
:
These results could also have been found from the second of equations
without making use of relations involving the time.
Example 4.
and now,
Heavy Symmetrical Top. In 6 we found
U=Dcos0,
Since
<f>
for the kinetic energy
in addition to this, let there be the potential energy
so that
and ^ are
oych'c variables,
we have
(11'),
43
(12)
and
In the equation for
we put
cos
0= M,
and obtain
frf<t
'
(13,
where
this is
a cubic in
u, so
the solution of (13) involves
elliptic integrals.
The Eulerian angles and may be expressed by similar elliptic integrals. If,
for example, we solve the equations (3),
6, for $ and ^, we obtain, taking (12)
<f>
into account,
/I
-
(Z
(JL
<V
AX J
Â z
2
h c>os
COS
A x sin 2
and
(14)
The evaluation the
as a periodic function
integral type (13) gives t/=i os
It oscillates backwards and forwards between two zero points
of the time.
of F, which enclose an interval in which

equal to a 3 we have
is
a2
is
not precisely
follows that,
somewhere in
positive.
If
and
A
both negative.
If
a motion
is
to be possible at
all it
+1), F must not be

negative ; it has then two zero points u
and w a which may coincide. If the zero
the interval
points
are
(1,
different,
it
means that the
point of intersection of the axis of the top

with a sphere, described about the centre
of the top, oscillates backwards and forIt
wards between two parallel circles.
describes a curve shown in fig. 1. In the
case of the double root our equations (13)

and (14) fail, but the motion can be easily
calculated in an elementary manner
the case of a regular precession.
FIG.
is
1.
then a constant, and we have
44
general rule for the rigorous solution of the Hamilton-Jacobi

cannot be given. In many cases a solution
differential equation (5)

is
obtained on the supposition that S can be represented as the
sum
of /functions, each of which depends on only one of the co-ordinates

q (and, of course, on the integration constants a 1 .
a/)
.
partial differential equation (5)
we
solve for
then resolves into
ordinary
form
differential equations of the
or, if
8=8^0 +...+SX?,).
(15)
The
-,
dq k
The
differential equation (5) is said in this case to
be soluble by
separation of the variables, or, for short, to be separable.

The case dealt with above, where all co-ordinates with the exception of one (y t ) are cyclic, can be regarded as a special case of this.
We make the hypothesis

and the
differential equation
/
as
becomes
ss\
"("*;*)-
which agrees exactly with
(11).
SECOND CHAPTER
Periodic Motions with
9.
WE have seen that,
One Degree
of
Freedom
in the case of systems of one degree of freedom,
new
variables <, a can be introduced in place of the variables

such that a is constant and <f> is a linear function of the time.
variables
way
</>
and a are
we can
q,
p,
The
not, however, determined uniquely in this

a by an arbitrary function of a, whilst
in fact replace
multiplied by a factor dependent on a.

For periodic motions it is an advantage to make a perfectly definite
and a. Now there are two kinds of periodicity. Either
choice of
</)
is
<f>
different values of q correspond to different positions of the system

and q and p are periodic functions of the time, and also of the
variable
^ which
there
a quantity
is
is
linearly connected with the time, in

o>
which case
such that
for all values of q ; or else the configuration of the system is the

same for any two values of q differing by a constant quantity,
which we shall take to be 2?r. This increase in q of amount 2?r
always takes place during the same time, and then

)
In the
first
case
we speak
=q((/>)
+27T.
of libration, in the second of rotation.
of these are the oscillating
Examples
pendulum respectively
pendulum and the rotating
(see below).
In both cases we shall choose ^ in a particular way, namely, in such

a way that it increases by 1 during one period of the motion, in which
case we shall denote it by w. Let the corresponding conjugated
We call w an angle variable and J an action variable.

consider S to be a function of q and J, then
variable be J.
If
we
w=
46
8,
(cf. (1),
remembering that
the quantities there written

of w along the path is
That the period of
w shall be
<
w and J are particular examples of

and a), and the differential quotient
therefore implies that
a fas
where the symbol $ denotes that the integration is to be extended

over one period, i.e. in the case of libration, over one back and forward
motion of q, and in the case of a rotation, over a path of length 27r.
We can clearly satisfy this requirement by putting
(i)
or, in
other words,
by making J equal to the
increase of S during one
period.
The variables w, J may

way.
If
therefore be introduced in the following
H is given as a function of some canonical variables q, p, the
action function
S=S(y,
is
a)
determined by integration of the Hamilton-Jacobi equation, and
the integral
J=(T)
dq
J fy
is
calculated as a function of a or
W. J
is
then introduced into S in
a or W.
means
of the transformation
By
place of
P=
=s J
+ constant would also satisfy the condition. The general transformation

(</>,
which
a)->(w, J)
the periodicity conditions postulated contains in fact another arbiIts generator is

trary constant in addition to the phases constant for w.
satisfies
The method for determining J given above

particularly usefu] in the quantum theory.
is
equivalent to putting
q =0
it is
47
w with the period 1, and

the canonical equations it
follows that for any one possible motion of the system
p and
q will become periodic functions of
H will be a function W of J alone.
From
J=constant
and
.
W
(3)
W
Since
we have chosen w so that it increases by
of the motion,
If
is
1 during each
period
a function which increases con-
v must be a positive number, it is equal to the

of periods in unit time, or the frequency of the motion.
tinuously with J
number
follows that
it
the variable
<f>
conjugate to a
is
already known, J can be found
from the equation
The equations
of transformation are then
OJ
consequence of the above determination of J as the increase in S

during one period, is that the function
S*=S-wJ
(4)
is
a periodic function of
w with the period
1.
Conversely this require-
ment may also be used for the unique determination of the magnitude
J,
which
is
fixed except for
an additive constant by $dw=l,
in
which
case equation (1) is obtained. In place of S the function S* can be regarded as the generator of the canonical transformation which transforms q and p into w and J Comparing the transformation equations
.
with equations (2
(2)
)of
7, it will
be seen that S
satisfies
the equation
whence
and this
implies that S*
is
the generator of the transformation
48
The
calculation of the integral J necessitates study of the connecand p as given by the equation
tion between q
HfopHW.
(6)
Let this relation be represented by a family of curves with the parain the (p, q) plane. The cases of libration and rotation are
meter
then represented by two typical figures
(figs.
2 and
3).
FIG. 2.
In the case of libration a closed branch of the curve
and J denotes the enclosed
area, which,
by
(6)
7, is
(19),
must
exist,
a canonical
invariant.
For rotation, p must be a periodic function of q with period 2?r, and

J denotes the area between the curve, the #-axis, and two ordinates
at a distance 2?r apart.
For the purpose of illustration
we
shall deal
with the case of
classical
mechanics on the assumption of a co-ordinate system at
By (8),
8,
In order that libration

root
must have two
may
zeros, q'
rest.
occur, the expression under the square
and q" between which it is positive
then
p vanishes only at the limits of the interval (q' q"). In order that a
closed loop may be formed from the two branches of the curv$ (6), it
9
dp
is
further necessary that -=- shall be infinite at
q'
and
y".
Now
dU
is not at the same
dq
time zero, i.e. provided g', q" are simple roots of the expression under
the root sign. In this case the resulting curve, which is symmetrical
about the q axis, will be traversed completely, and always in the same
the condition
sense.
is
Then, by
therefore fulfilled, provided
(8),
5,
49
is always positive ; therefore on the outward journey

the
(dq>0)
upper branch (p>0) will be traversed, and in the return
the lower branch (p<Q)
(dq<Q)
journey
and thus pdq
be followed. The co-ordinate q traverses the whole region between the zero
these zero points form
points q' and q"
will
the limits of libration.
be varied, the corresponding

within one another, without
If
be decreased, the
intersecting.
Fia 4>
zero points move towards one another
and converge to a point, provided no new zero points occur between them. This point we call the libration centre at it
If
curves
lie
It corresponds to a state of stable equilibrium of the system, since the

movement resulting from slight alteration of the initial conditions re-
new zero points occur between q' and q", they
mains in its vicinity.
If
coincide at their
appearance as
first
is
decreased, and here too
"-0.
dq
In this case the state of equilibrium is unstable, since, for a small

variation of W, the motion does not remain in the immediate vicinity
of the equilibrium position.
If
be increased it may
d\J
vanishes, in which case
happen that at
q'
we again have a
dq
or q" the derivative
condition of unstable
it may also happen that the

equilibrium. For such values of
motioi? approaches the state of unstable equilibrium asymptotically
with the time. The motion is then said to be one of limitation.
may occur, must first of all be

in
we
and
assume
as
further, the quantity
periodic
q,
period 2?r
under the root sign must always be positive.
In order to illustrate these ideas we consider the pendulum, for
In order that rotational motion
which
occur.
all
three possibilities
We have
(see (10),
8)
cos q
the curves
For
(6)
and limitation
rotation, libration,
D>0
have therefore the form shown in
fig. 5.
50
the curves contract on the libration centre
=0. For
-D<W<D
we have libration between the limits
1
j*=-coB- (--D/W).
For
W>D,
on the other hand, we have rotation, the pendulum rotating always
in the same direction. In the limiting case
approaches asymptotically the position 377.
it
71
FIG.
5.
In this case the integral
J=(()V2A\/W+D cos qdq
(7)
for the libration
is an elliptic integral.
Only in the case when
close together (on the two sides of the libration
motion
the libration limits
lie
centre) can it be approximated to by a simple integral. The calculation then corresponds to that for the linear harmonic oscillator, to
which we now turn.
Linear Harmonic Oscillator. In 7 we have already found the
and a, and according to (18), 7, q has the period c5=27i in
The
variables w and J are introduced in accordance with the formulae.
Example.
variables
</>
</>.
ad</)
and
51
where
The motion
will
now be
represented by
q= 2n
(
\mv/
2nw
sin
(2m vJ)* cos 2nw.
The energy becomes

from which the relation
at once evident.
is
In order to show how the change to angle and action variables can be made
without a knowledge of and a, we shall once again carry out the calculations
for the oscillator, starting out from
<
H =.+?y.
2
2m
we put
If
this expression equal to
where, for shortness,
we
W,
write
then
2W
_
__
fi
MO) 2
From
this it will
We
be seen that the libration
by introducing the
auxiliary variable 0,
by means
q= a sin
</>
to
goes frern
limits are situated at q
=+
and
calculate the integral
2n during one
of the equation
<
period of the motion.
J=^f%os
Jo
(*>
We obtain
= -?W
o>
and, consequently, the energy or the Hamiltonian function
is
given by
W=H=vJ,
(8)
where we have put
a)2nv.
To
express the co-ordinate q in terms of the new variables w, J, and hence in

terms of the time, we do not need to calculate S itself.
have
We
in which
is
to be considered as a function of q and
p= (2mvJ
J:
52
We obtain
I
mvdq
_1
/2jr 2vm\*
or
where
We then have for ^

(
10)
For the pendulum with small amplitude the corresponding formulae are
10.
The Adiabatic Invariance
of the Action Variables
and
Quantum Conditions for One Degree of Freedom

Now that we have considered in detail the mechanics of periodic
systems with one degree of freedom we can pass on to the question
how, and how far, the mechanical principles may be applied to the
the
mechanics of the atom, the chief characteristic of which
is
the
existence of discrete stationary states.

have a typical example of this application in Planck's treat-
We
of the simple linear oscillator (see

1). The stationary states
the
were defined there by the condition that
energy should have only
the discrete values
ment
W=n.hv
(1)
The question now occurs whether
way with
it is
(n=fi
1,
.)
possible to deal in a similar
the general case of periodic systems of one degree of
freedom.
In the development of the mechanics of the atom the method of

discovery has been to retain the classical mechanics as far as possible.
Planck's theory of the oscillator, for example, is based on the view
that the motion of the vibrating particle takes place entirely in
accordance with the classical principles. Not all motions, however,
with arbitrary
initial conditions, i.e. values of the energy, are equally

certain
motions, characterised by the energy values (1),
permissible ;
a
occupy
preferential position in the interaction with radiation, on
account of a certain inherent

"
stitute the
stationary states."
The endeavour to
"
"
stability
these motions con-
retain the classical mechanics as far as possible
53
method, we take as our first requirean atomic system shall be calwith the laws of classical
accordance
in
as
far
as
culated,
possible,
of
radiation
is disregarded. For
the
classical
but
mechanics,
theory
this requirement to be fulfilled it is essential that the motion shall
"
"
be of such a nature that the term state is applicable to it. This
would not be the case, for example, if the path went off to infinity or
if it approached a limiting curve asymptotically. In the case of
periodic motions, however, the system may well be said to be in a
having proved to be a
fertile
ment that the stationary
definite state.
We
states of
shall see later that there is still a further class
of motions, the so-called multiply periodic systems, to which the

same applies. On the other hand, the development of the quantum
theory has shown that these probably exhaust the types of motion
for which classical mechanics gives a valid description of the station-
ary states we shall restrict ourselves in this book essentially to this

domain.
The next question concerns the manner in which the stationary
motions are to be selected from the continuous manifold of those
;
mechanically possible motions. We shall first try to give an answer

to this in the case of periodic systems with one degree of freedom.
At first sight we might be inclined to apply to the general case the
formula
(1)
established for the oscillator.
Since, in general, v
is
W, a transcendental equation would have to be solved to

determine W. This method of procedure must, however, be rejected
function of
it
leads in certain instances to results which are in contradiction
with observation
(e.g.
in the case of diatomic molecules, the atoms
of which are coupled non-harmonically with one another) and, further,

it
cannot be sustained theoretically.
The quantum conditions by means of which the stationary orbits

are selected can be expressed in the form that a certain mechanically
defined magnitude is an integral multiple of Planck's constant h. In
the case of the oscillator this magnitude is W/i/ the question is, what
;
to take the place of this quantity in the case of other systems ?

now examine the conditions to be satisfied by a magnitude in
"
order that it may be quantised in this manner. In the first place
is
We
' '
must be uniquely determined and independent of the co-ordinate

system. This, however, would do but little to narrow the choice, and,
if nothing more was known, the results of a comparison of the theory
with observation would be our sole guide. In this connection Ehren-
it
however, done much for the development of the quantum

theory by advancing a postulate which makes possible a purely
theoretical determination of the quantum magnitudes.
fest has,
54
The novelty
of Ehrenfest's idea lies in regarding the
atoms not as
We
have posisolated systems, but as subject to external influences.

tulated above that classical mechanics shall be valid for isolated systems in the stationary states following Ehrenfest, we now require
that classical mechanics shall also be retained as far as possible in the
;
presence of external influences.

We must now investigate to what extent this
is
possible without
with the principles of the quantum theory.

According to these the magnitude to be quantised can change only
by integral multiples of h. If, therefore, an external influence is not
sufficient to cause an alteration of magnitude h, the quantum magni-
coming into
conflict
tude must remain absolutely unaltered.

It is first necessary to find the conditions which determine whether
the external influence is capable of causing such an alteration (known
It is known from experias a quantum transition or jump) or not.
ence that quantum transitions can be caused by light and by molecular impacts. In these cases we have to deal with influences which
vary very rapidly. If we consider, on the other hand, actions which
change very slowly
slowly, that is to say, in comparison with the
atomic systems- e.g. the switching on of

processes occurring within
electric or magnetic fields, experience teaches us that in this case no
neither emission of light nor other
transitions are excited
quantum
with
processes associated
quantum transitions
are observed in such
cases.
The quantum transitions certainly take place in a non-mechanical

The maintenance of the classical mechanics, required by
Ehrenfest in the case of external influences, is then possible only if no
manner.
quantum
transitions are excited
by these
influences,
i.e.
only in the
case of processes which vary very slowly.

Ehrenfest calls this postulate, that, in the limiting case of infinitely
slow changes, the principles of classical mechanics remain valid, the

adiabatic hypothesis, by analogy with the terminology of thermo*
Bohr speaks of the principle of mechanical transform-
dynamics
ability.
This postulate severely restricts the arbitrariness in the choice of

the magnitude to be quantised. For now only those quantities are
to be taken into account which, according to the laws of classical
mechanics, remain invariant for slow variations of external influ"
ences ; following Ehrenfest, we name them adiabatic invariants."
Kon. Akad. Amsterdam, vol. xvi, p. 591, 1914, and Ann. d. i'hystk, vol. li,
"
"
Ehrenfest found his adiabatic hypothesis in an altogether different
way, namely, by an examination of the statistical foundations of Planck's radiation
1
Proc.
p. 327, 1916.
formula.

In order to
make
55
clear the conception of adiabatic invariance, we

pendulum consisting of a bob of
consider the example of a simple
mass
on a thread whose length
I is
slowly decreased by drawing
the
of
up through
point
suspension. This shortening
causes an alteration of the energy
and the frequency v of the
we
can
that
for small oscillations the
show, however,
pendulum
invariant.
remains
magnitude W/v
the thread
The
which keeps the thread of the pendulum taut consists of a

gravity component mg cos </>, and the centrifugal force ml</>*, the
angular displacement being <. The work done then during a shortenforce
ing of the thread
is
A=
$mg cos
2
<l>dl
$ml(J>
dL
If this shortening occurs so that its progress in time has no relation to

the period of oscillation, and sufficiently slowly for us to be able to
ascribe an amplitude to each single period, we can write
dA =
mg cos <fxll
where the bar denotes an average taken over one period. For small
oscillations we can write
cos
<=-
an expression
mgdl, which
the
done
in
of
the
work
raising
position
equilibrium of
represents
the bob of the pendulum, and a second expression
If this is substituted, rfA resolves into
which denotes the energy communicated to the oscillation

values of the kinetic and potential energy of the
same, and are thus equal to half the total energy
T"
are the
T-2^-2^
Substituting,
The mean
pendulum
W m
1
'
we have
Since
now
the frequency v
is
proportional to
dv
dl
and
therefore
56
follows that
it
This differential equation expresses the way in which the energy of

oscillation is connected with the frequency for an adiabatic shortening,
and
it
follows
by
integration that
=constant
v
as asserted.
A similar argument applies when

external influence.
v is slowly varied by some other

Since the harmonic oscillator is mathematically
equivalent to a pendulum with an infinitely small amplitude of oscillaW/F is constant in that case also Planck's quantum condition
tion,
consequently in agreement with the adiabatic hypothesis. It

can be shown, on the other hand, that for other periodic systems of
(1) is
one degree of freedom
W/v
is
not an adiabatic invariant.
We remember that, according to (8),

oscillator the
magnitude W/v
is
9,
in the case of the harmonic
also the action variable J.
This
suggests
3=nh
(2)
of one degree of freedom.

the
of
The quantity J
requirement
uniqueness, since it is indethe
co-ordinate
system (on account of the invariance of
pendent of
as a general
quantum condition for systems

fulfils
and we shall show now that it is an adiabatic invariant.

The general proof of the theorem of the adiabatic invariance (or,
as Bohr calls it, of the mechanical transformability) of the action
variables was carried out by Burgers x and Krutkow, 2 who at the
same time treated the case of several degrees of freedom. 3
tfdpdq,
cf
7),
We think of a mechanical system of one degree
of
freedom subject
This can be expressed by introducing in

to an
in
addition to the variables, a parameter
of
the equation
motion,
a(t) depending on the time. We consider now an adiabatic variation
external influence.
of the system to be such that it has firstly no relation to the period

of the undisturbed system, and secondly, that it takes place suffi-
We
assume
ciently slowly for a to be regarded as indefinitely small.
further that, for a certain range of values of a, the motion for con-
d.
J.
S.
M. Burgers, Ann. d. Physik, vol. lii, p. 195, 1917.

Krutkow, Proc. Kon. Akad. Amsterdam, vol. xxi, p. 1112, comm. 1919.
8
Other proofs on more general assumptions have been given by M. v. Laue, Ann.
Physik, vol. Ixxvi, p. 619, 1926, and P. A. M. Dirac, Proc. Roy. Soc., vol. cvii,
p. 725, 1925.
57
and that we can introduce angle and action varithen have the theorem
The action variable J is adiabatically invariant, provided the
stant a
ables
is
periodic,
and
We
J.
frequency does not vanish.
The Hamiltonian function

tt(p, q, a(t))
dependent on the time

but the canonical equations
is
the energy therefore
are
still
We
P==
a/
8q
valid.
imagine
now
the canonical transformation carried out which
transforms, for constant a, the variables q,
7,
p into the angle and action
It is useful to write the transformation in the
variables w, J.
(c/. (1),
not constant,
.an
.an
=
is
and
(5),
form
9)
as*
dw
The function S* depends on the parameter a in addition to the variand w S* is therefore dependent on the time and, by (1),
ables q
7,
becomes
.
dt
The transformed canonical equations are therefore

an a/as*\
j=
Since
_l -^).
H depends on the action variables only

___^/as*\
_^>_/as*\
in which the differentiation with respect to t and a is to be carried

out for fixed values of q and w, and the differentiation with respect
The change of J in a time interval (t l9 2)
to
for fixed J and a.
will
be
a
58
Since the variation of a is supposed slow and not connected with

the period of the system, a can be brought outside the integral sign.
We shall carry out the proof of the invariance of J by showing that
of the order of
is
magnitude
d(t 2
t l)
for
from this
and for
in the limit of infinitely slow variation (d->0)

the variation of J becomes zero.
Since (by
;
9)
S*
is
it
follows that
finite d(t 2
a periodic function of w, the same
this remains true
if
we
is
introduce the variables w, J,
t 1 ),
true of
The
a.
da
integrand of
(3) is
therefore a Fourier series
without a constant term

tion sign).
If
we
write
estimated becomes
(this
we
signify
by the dash on the summa-
w as a function of the time, the integral to be
The integrand is no longer exactly periodic in

depend on #, which varies with t however,
;
of a certain instant of time,
=0
as the
AT 's,
v,
and
powers of the alteration in a from its value

this alteration is small, as the expansion is not going to be
and 8 can be expanded

at
which we
in the neighbourhood
can take as =0, the T 's v9
in
t
greater than the periodic time T, and a is to be
taken so small that the variation of a in a period of the undisturbed
motion is small. Indicating differentiation with respect to a by a
dash, and values of the A T 's, v, and S for the value of a at t==0 by
used for values of
suffixes zero, the integrand
then becomes
(4)
If we integrate this expression over a period of the first term, we

We now
obtain expressions of the order of magnitude dT and dT 2
at
carried
of
out
the
the
the
interval
beginning
imagine
expansion (4)
.
(t l9 1 2 )
and the
integral taken over one period of the first term.
We
then imagine a new expansion (4) carried out at the beginning of the
remaining interval and the integral taken once more over one period
of the first term. We continue this process until the interval (t^ t 2 )

used up.
The
59
not be taken over

magnitude even when t^t l is indefinitely great. It is seen that if T remains finite over the whole range
of integration, i.e. if v does not vanish, the whole integral will be of
the order of magnitude d(t 2 tj).
We have proved by this the adiabatic invariance of J. On the
basis of this invariance, and the special result in the case of the
oscillator, we are led to the choice of J as the quantity to be quantised
in general. This assumption has been confirmed by the further
is all
full
period
it
last integral will, in general,
has a
finite
development of the quantum theory.
way
We
state
it
in the following
Quantum
Condition.
In the stationary states of a periodic system
with one degree of freedom the action variable

of h:
is
an integral multiple
The energy steps, as functions of the quantum number

determined by this quantum condition. 1
The experimental method
of electron impact,
n, are also
mentioned in the
introduction, enables the energy levels of the atomic systems to be

determined in a purely empirical manner. Comparison of these
determinations with the theoretical values provides a test of the

foundations of the quantum theory as far as they have hitherto been
developed.
As mentioned in the introduction, the interaction of the atomic

systems with the radiation is governed by a further independent
quantum principle, Bohr's frequency condition,
which determines the frequencies of the emitted and absorbed light.

(1)
and (2) denote here the energies of two stationary states and v
the frequency of the light, the emission or absorption of which is
coupled with the transition of the system from the state 1 to the state
(2)
our formula gives a positive i>,
2. In the case of emission (W(1) >
)
(2)
(1)
a
of
in the case
)
negative v.
absorption (W
W
<W
A much more rigorous test of the quantum rules is made possible by

applying Bohr's frequency condition to the frequencies of spectral
lines.
1
This quantum condition was given first in geometrical form by M. Planck,
It is
160.
Vorlesungen iiber die Theorie der Wdrmestrahlung, first edition, 1906,
to be found also in P. Debye, Vortrage uber kinetische Theorie der Materie und, der
(Wolfskehl Congress), p. 27, 1913.
60
The Correspondence Principle

of Freedom
11.
for
One Degree
The fundamental postulate of the stability of atoms referred to in

the introduction is satisfied by the two principles of atomic mechanics
given in 10. We now inquire to what extent they are in agreement
with the other fundamental postulate, that the classical theory shall
appear as a limiting case of the quantum theory.
Planck's constant h occurs as a characteristic magnitude in both
quantum
tum
and is a measure of the separation of the quanOur requirement signifies that the quantum laws shall
principles,
states.
tend into the
classical ones as limits as A-^0
steps then converge to the
continuum of the
the discrete energy
classical theory.
The
we have to see
frequency condition requires special examination
if the frequencies calculated by it agree in the limit with those to be
:
expected from the classical theory.

The radiation from a system of electrically charged particles with
charges e k at the points r is determined, according to the classical
fc
theory,
If
ing
by the
electric
moment
the energy radiated in the course of one period is small, the damppresent be neglected. For a system of one degree of
may for the
freedom, such as we consider here, the rectangular co-ordinates of the

charged particles will be periodic functions of
with the period 1. Since the same will hold for p, each component of
the electric moment may be developed in a Fourier series of the type
The C T 's are complex numbers since, however, the electric moment is
real, the C T 's and C_ T 's must be conjugate complex quantities.
;
On this basis the time variation of the
electric
moment can be con-
sidered as a superposition of harmonic oscillations with the frequency

TV
the amplitudes of the corresponding partial oscillations of the
;
moment
are given by the values of CT and their energies are pro2

According to the classical theory
portional to the values of C T
the r-th oscillation component would give rise to a radiation of
|
frequency
*
(1)
1
=TV - T0W_dW
-8J ~djTr
T as well as i always occurs in the Fourier expansion, the sign of the

expression for the classical radiation frequency has no significance,
Since
We
compare with
If
this the
quantum frequency
61
the quantum number n decreases by r in the quantum transition
under consideration, then
AJ=J 2 ~J =(^ 2
1
so that
we can
rh,
AW
~
(
n^h,
write
"* W
'
If
we proceed to the limit
A->0, or AJ/r->0, then (2)
and
(1)
become
identical.
For the case

frequencies (1)
of a finite
h we can state the relation between the two
and
The quantum
(2) as follows
theory replaces the classical differential coefficient
:
by
We
do not proceed to the limit of infinitely

small variations of the independent variables, but stop at finite intervals of magnitude h.
The transition between two neighbouring quantum states for which
a difference quotient.
"
"
associated with, or
to, the classical fundacorresponds
mental vibration a transition in which n changes by r corresponds
to the classical rth overtone VTV.
r=l
is
This relation between classical and
quantum
frequencies forms the
substance of Bohr's correspondence principle.

According to this correspondence the quantum frequency v is, in
general, different from the classical frequency TV. If, instead of proceeding to the limit #->0, we go to the limiting case of large quantum
n, and consider only such changes of n as are small comwith
the value of n itself, then, on account of the monotonic
pared
character 2 ( 9) of the function W(J), the difference quotient will
very nearly coincide with the differential coefficient and we obtain
numbers
the approximately correct equation
v=^rv=(n l
n 2 )v,
(n l large,
n1
w 2 small compared to n t ).
n 1 n 2 is no longer small in comparison witt n l9 then the agreement between the classical and quantum frequencies will not be so
good. For a given n t the correspondence between the frequencies in
the case of emission (n^>n^ has a limit, inasmuch as r=n l w 2 cannot be greater than n v
If
1
Positive v in the expression for the frequency given by the quantum theory
denotes emission, negative v absorption.
8 A
function of one variable is said to be monotonic when its differential coefficient has the same sign for all relevant values of the independent variable.
62
The two quantum principles hitherto given do not, however, provide a complete description of the radiation processes.
light wave
is characterised not only by a frequency, but also by intensity, phase,
and
state of polarisation.
The quantum theory
is
at present unable
to give exact information with regard to these features. Bohr has,

however, shown that it is possible, by extending the correspondence
from frequencies to amplitudes, to make at any rate ap-
principle
proximate estimates regarding the intensity and polarisation.

In order that, in spite of the totally different mechanism of radiation, quantum theory and classical theory may give, in the limiting case of large
quantum numbers
(or in limit A->0), radiations
with the same distribution of intensity among the component

oscillations, it must be assumed that in this limiting case the Fourier
coefficients
the
CT
quantum
represent the amplitudes of the emission governed by

theory. Thus the values of CT must be related to the
probabilities of the transitions necessary in order that the energy

principle may remain valid. By considering the different components
moment p a determination of the polarisation propercan be made at the same time as that of the intensities.
of the electric
ties
The case CT =0
case there
is of especial
importance, for here in the classical
no emission of the corresponding frequency, so the
is
transition should not occur.
corre-
Since, however, the
sponding quantum
correspondence principle only gives a relation between radiation
phenomena on the classical and quantum theories the results de-
duced from it concerning the possibility of quantum transitions hold

only in those cases where the atomic system is interacting with radiation. They need not hold for impacts between atomic systems.
On the basis
difficulties
of the correspondence principle we can deal effectively with the

which we have met with in the introduction ( 1, 2) in the case of the
resonator.
The expression
variables
by
is
(9),
for the displacement q as a function of tho angle
J
__
\*
=(2
sm xnw
a Fourier series with only the one term T= 1, according as we

take the positive or negative root. According to the correspondence principle,
therefore, the quantum number can, in the case of the resonator, change by 1
this is clearly
only, giving
v=v.
The correspondence principle leads then to the result that a resonator behaves
on the quantum theory, as far as the frequency of its radiation is concerned,
exactly as it would do according to the classical theory. In the case of other
atomic systems, however, we shall see that this is by no means the case.

12.
63
Application to the Rotator and to the Non-harmonic

Oscillator
].
THE ROTATOR.
where
By
6,
(1),
the Hamiltonian function
p is the momentum conjugated to the
signifies
angular momentum.
is
angle of rotation 0, and
In this case
J =^>pd(f>=
since the system assumes the same aspect each time
increases by
27T.
The energy, as a function of the action variable, and then of
<
the
quantum number m, becomes
W=H
(1)'
v
and the angle variable
is
where
This calculation can be applied to the motion of diatomic molecules
and concerns two classes of phenomena the theory of the rotation

band spectra of polar molecules and the theory of the specific heats
of gases. The simplest model of a diatomic molecule is that known
as the dumb-bell model the two atoms are regarded as massive particles at a fixed distance I apart, and it is assumed that the structure
rotates^ with moment of inertia A, about an axis perpendicular to the
:
atoms.
rigorous foundation for these assumptions
of
the
about the axis joining the atoms and
the
rotation
(i.e.
neglect
the assumption of a rigid separation) and their replacement by more
general assumptions will be given later.
line joining the
(a)
THEORY OF ROTATION BAND SPECTRA. We assume that the

moment (e.g. we regard HC1 as a combina-
molecule has an electric

tion of the
H+ and Cl~ ions), in which case it would, according to the
classical theory, radiate light of
frequency
0J
Overtones do not occur.
If
47T
the particles have the charges e and
e,
64
moment p
the components of the electric

are
in the plane of the rotation
x l )=el cos 2irw
P*=(a?a
P=2
/i
=e
sin
two signs correspond to the two possible directions of

The expressions for the components of p in terms of w con-
in which the
rotation.
T=
1.
tain therefore only one Fourier term each, r=I or
should expect that such a molecule, possessing an electric moment, would radiate according to the quantum theory the quantum
We
differ
from the
frequencies will, however,

of the stationary states are given
classical ones.
The
energies
by ) Since only one Fourier term

in
the
motion
the
occurs,
quantum number can change by +1 or 1
and
the
Bohr
only,
frequency condition gives therefore for the emission
(m+l)->m
If this
it will
1
(
formula be compared with that for the classical frequency
be seen from the relation

1
2m
that the relative difference between the two frequencies will be the
smaller the greater the value of m.
Except
for a small additive constant difference in the frequencies,
the classical theory and the

the same results in this case
quantum theory both
lead to essentially
each gives a system of equidistant lines

in the emission and absorption spectrum. This is the simplesfccase of
;
the empirical band formula first found by Deslandres. It is easy to

see that these lines are to be sought for in the infra-red. In the case of
atom of mass 1*65 X lO^ 24 gm. essentially

HC1, for instance, the light
rotates about the much heavier 01 atom at a distance of the order of
magnitude of all molecular separations, say a Angstrom units or
a 10"8 cm., a being of the order of 1. The moment of inertia will
then be
.
A=a
the frequency of the
2
.
1-65
X 10-40 gm. cm. 2
first line
5X10 11
v
sec -i
65
and the wave-length

f
A=-=0-06a 2 cm.
v
Since a
of the order
is
1,
we have to
deal with lines on the farther side
of the optically attainable infra-red. These pure rotation bands have

been observed in the case of water vapour (for example). In the case
of a large
number
of gases,
bands have been found which are due to
the combined action of the nuclear oscillations and rotation
these
of equidistant lines, but are situated in the

shall deal with the theory
shorter wave-lengths.
region of much
of them further on
We
19, 20).
HEATS OF ROTATION OF DIATOMIC GASES.
(b)
same type
exhibit the
The dumb-bell
molecular model leads also, as is well known, to the correct result

in the theory of specific heats at high temperatures.
Three translational and two rotational degrees of freedom are ascribed to such
a model
counted.
which
is
the rotation about the line joining the atoms is not

According to the theorem of equipartition of energy,
deduced by applying statistical mechanics to classical
systems, the mean energy |AT is associated with every degree

freedom without potential energy, and consequently the total
energy -|T would be associated with the five degrees of freedom
of
mentioned
the molecular heat
is
therefore !>R.
shown experimentally that the molecular heat
of
Now Eucken l
has
hydrogen decreases
with decreasing temperature

for T=40 abs. it reaches the value
and subsequently remains constant. Hydrogen changes then,
its rotational
in a sense, from a diatomic to a monatomic gas
2
has
energy disappears with decreasing temperature. Ehrenfest
;
|R
given the elementary theory of this phenomenon. The mean energy

which can exist only in the quantum states (1), is
of a rotator,
w,=^r
m=i
where
If
the values
1
A
P.
be substituted for
W m we shall have
Eucken, Sitzungsber. d. Prtusa. Akad. d. Ww., p. 141, 1912; see also K.

W. Heuse, Ibid., p. 44, 1913 Ann. d. Phytiik, vol. xl, p. 473, 1913.
Ehrenfest, Verhandl d, Deutsch. Physical. Get., vol. xv, p. 451, 1913.
Scheel and
2
(1)
66
m=0
where
*'
Ehrenfest calculates the heats of rotation by assuming for the mean

energy of a molecule twice the mean energy of one of our rotators,
because the molecule has two perpendicular axes about which

rotate. The heat of rotation per gram molecule is then
it
can
*-f
We
examine the behaviour of
this expression for
peratures.
For small values of
the series for
low and high tem-
T we have large a thus er* is very small, and

Z may therefore be broken off after the first two terms
;
Z-l-Hr*
log
7=0-*,
consequently
c^RaV-*,
and this expression tends to zero with decreasing T (increasing cr).
For large values of T, o is small, and then the sum in the expression
for Z may be replaced by an integral
Z=J
log
Z=
e-*
\lm=-lj-
% log or+coristant,
consequently
c r =R.
The heat of rotation gives rise therefore, with increasing temperaan increase of the total molecular heat from 211 to R.
ture, to
Ehrenfest's theory can, of course, give only a rough approximation

to the actual state of affairs, since the two rotational degrees of
more rigorous infreedom are not independent of one another.
vestigation must take account
of the
motion
of the molecules in
space.
2.
THE NON-HARMONIC OSCILLATOR.
of a linear oscillator of slightly
We
shall consider the case
non-harmonic character,
i.e.
with a
1
See the detailed treatment by F. Eeiche, Ann. d. Physik, vol. Iviii, p. 657, 1919,
or see C. G. Darwin and R. H. FoVler, Phil. Mag., vol. xliv, p. 472, 1922.
67
system of one degree of freedom for which the Hamiltonian function

is
given by
H=
(3)
+-
to
ri
where a
is
small.
Our first object will be to find the relation between the action variable J and the energy \V in the form of an expansion in powers of a.
We have
where
We
write this in the form
For small values of
a,
two
roots,
which we take as
el
and
e 2 lie in
,
the
I~2W
neighbourhood of
them
ib
V/ mo)
the third root, e3
is
-,
and the motion takes place between
large
compared to
e l? e 2
and has the
opposite sign from a (af(q) must be positive for values of q lying

between e^ and e 2 ). We write therefore
(5)
and obtain the following expansion
for
y=*i^J.~3
~J
+...};
where
We
transform these integrals by means of the substitution
Appendix
(cf.
II)
(6)
If g oscillates
from one the libration

77
back,
increases from
~
2
to
77
+27r.
limits e
to the other e 2 and
We then find
68
-_
2
+-
2p2ff
^ cos
sin
J
on inserting the values
or,
To determine the
vanishes.
find for
We
_e
\ 2/27r
sin 2
+(\ -^T2
iA
cos 2
1 J
"|
of the integrals,
e i) a
and then
-* c ia]
'
J o-
roots e^ and e 2 we write q as a power series in a

of the coefficients the polynomial/ (q)
what values
thus find
where
_5
2
To obtain the third
root
we
find for
es
If
W
If
=-a
+ -a +
we
somewhat lengthy
further substitute the
first
calculation,
15
approximation
W(
W = -J=VoJ
T
W
>T
for
these expressions into the equations for
after a
W/
If
.
2
we now introduce
and J 2 we obtain,
coefficients in
We thus find
the function /(g) vanishes.

(8)
what values of the
W within the brackets, we get
finally
It will thus be seen that the frequency
69
v= -
is
not V Q but, to this

,
uJ
degree of approximation,
15
In the case of radiation from an atomic system which
may be repre-
sented approximately by a non-harmonic oscillator it becomes of

importance to determine which transitions between the energy steps
given by
(9)
are permissible according to the correspondence principle.

this, we calculate q as a function of the angle variable
In order to find
The
w.
latter is given
by
w _aS
rdp
fm dWc
~w jan v 2^
and
thus,
from the expansion

/
V
__
*2ae3
d\V
dJ
/~~
V
The
'2ae^
(AV
we have,
(5),
to the order required,

/
dq
V(e 1
"
/K
dJ\
e 2 )\
q)(q
^
"2c.
integrals
=
.=
also be calculated
by means
__
t
l
may
dq
rfjj
V^-qKq-
of the substitution (6), their values
being
If
now we
we
substitute the values (7)
and
(8)
found above for
get
1
...
]
If
we now
2
neglect the terms in a
we can put
and obtain
(10);
w=J-L +a
27r
2l/
V 2w m
6
cos
e l9 e 2 ,
70
It follows
from
(6)
and
(7) that,
2
neglecting terms in a
q=aq 1 +q
where sin
iff
may
be calculated from
()
smifj
(10).
To the same order we
get
a-
q=q Q sin %TTW
?o
-(3
*
and finally
(
1 1)
=^
2nw
in
<ir
2 (3
of the co-ordinate q from its value in the case of the

0) is of the order a, whereas the energy
2
The mean value of the co-ordinate will
difference is of the order a
The deviation
harmonic
oscillator (#
not be zero, but to our degree of approximation will be given by
w
Jn the case of the non-harmonic oscillator, therefore, the co-ordinate
oscillates about a mean position differing from the position of equilibrium.
first
of
The
oscillation is not
which has an amplitude
harmonic, for overtones occur, the

of the order a.
On
the basis of the correspondence principle, the appearance of

overtones in the motion of the system implies that quantum transitions are possible for which the quantum number alters by more
than one unit.
number
of 2
is
The probability
2
of the order a
(i.e.
of
an alteration in the quantum
the square of the amplitude of the
corresponding oscillation).
The fact that the mean value of the displacement does not vanish,
but increases in proportion to the energy, has been used by Boguslawin explaining the phenomena of pyroelectricity. He imagines
the (charged) atoms of a polar crystal bound non-harmonically in
ski
equilibrium positions, so that with increasing temperature (i.e.

energy) a mean electric moment will arise. In his first calculation
Boguslawski took for the mean energy the classical value JfeT but later
introduced the quantum theory by using for the mean energy Planck's
resonator formula ((5),
1).
Boguslawski, Physikal. Zeitschr., vol. xv, pp. 283, 569, 805, 1914. The problem
non-harmonic oscillator was first considered by Boguslawski, in an attempt to
explain pyroelectricity by means of the quantum theory. The phase integral is
actually a period of the elliptic function belonging to f(q) and may be represented
In the physical application,
exactly by means of hypergeometric functions.
Boguslawski restricts himself to small values of a, and arrives at the same final
formula as that given in the text.
1
S.
of the
71
The theory of the non-harmonic oscillator finds a further application in the explanation of the increase in the specific heat of solid
bodies at high temperatures above Dulong and Petit's value, 1 and
also in the explanation of
band spectra
(see
20).
Multiply Periodic Functions
13.
Before we can proceed to apply our results to systems of several

degrees of freedom we must introduce the conception of multiply
and examine some
periodic functions,
Definition
variables x
1..
xf
function F(x x
with the period
.
0> 2
>!,
of their properties.
.
a>
.
xf y 1
is periodic in the
.)
having the components
,
0) f ,
if
x / +a / )=F(a 1> x 2
xf )
F^J+O)!, x 2 +oj 2
xf
identically in x t
If x l9 x 2 ... xf be considered as co-ordinates in /-dimensional space,
.
(1)
each period corresponds to a vector in this space.

xf ) be replaced by (XiS> l9 x 2
If in (1) (x l9 x 2
&2
xf a) f ),
and this operation be repeated indefinitely, the truth of the following
theorem will be found to hold.
Theorem 1. A function which has the period o> has also the
.
period
is
the period with the components TO^,

an arbitrary integer (positive or negative).
the function
F has the period

x2
xf ) in
by replacing
that the following also holds.
(x l9
Theorem
2.
The
vectorial
(1)
a/, in addition to
of
two periods
To> 2
o>, it
by (Xi+tii, x 2 +& 2
sum o>+o/
TO), i.e.
where r
If
will
o>
TO)/,
be seen,
xf +a>/),
and
a/,
i.e.
the vector having the components
likewise a period.
is
By combining the
Theorem
3.
If
theorems
and 2 we have the general
a function has several periods
then every integral linear combination of these periods

1
M. Born and E. Brody, Zeitechr. /. Physik, vol. vi, p. 132, 1921 for detailed
of literature, see M. Born, Atomtheorie des fcsten Znstandes, Leipzig, 1923,
;
list
p. 698.
72
(2)
likewise a period.
is
Two
Definition 2.
be equivalent
if
points (Xj
the vector joining
#/)
and
them
is
x/) are said to

T *^
of the form
(x,'
'
A;
In order to eliminate trivial exceptional cases we add the condition
F shall possess no infinitely small

which
the
length of the representative vector is
periods,
smaller than any arbitrary number.
We shall consider now two periods o> and Ao>, represented by
parallel vectors, in which case A must be a rational number, otherwise the period (r-fr'A) & could, by a suitable choice of the in1
tegers r and r', be made arbitrarily small.
If now q is the smallest denominator by means of which A may be
expressed in the form p/q, p and q being integers, then &lq is likewise
a period, for by a theorem in the theory of numbers we can always
The function
Condition.
i.e.
none, for
find
two
integers r
and
so that
r',
and so
We
see
now
that
we can express each period whose vector has a
an integral multiple of a certain minimum one.

theorem may be deduced a generalisation which is
certain direction as
From
this
valid for all periods of a function F. In order to derive it we shall

suppose all the periods arranged in order according to the magnitude
of their vectors
:
o>
(3)
<L
a>'
<;
<L
o>"
We select the first period of this series together with the next one
having a vector in another direction. These two periods, which we
now call a)W and a>< 2 >, define a parallelogram mesh in the plane of
the corresponding vectors, with this property, that each vector
which joins two points of intersection of the net also represents a
period.
In this
way we can account
for all periods whose vectors lie in

there were a vector <, the end point of which did
not coincide with a mesh point (see fig. 6), then there would be a
this plane, for
mesh point
if
at a distance less than
o>(
2)
See Appendix
from that end point.
I.
If
73
were a period, then the vector represented by this separation would

likewise be a period ; its magnitude would, however, be smaller than
oV 2
which
To a>W and
the series
and
o><
2
),
contrary to supposition.
2
we now add the immediately succeeding period in
whose vector does not lie in the plane defined by
is
|,
(3),
o><
and
>
call it
dV 3 ).
These three periods determine in this way a threedimensional lattice, possessing the property that
/?;
each vector joining two
#/^
/
lattice points corresponds
to a period.
In this
way
^/
^/
periods are accounted

whose vectors lie
for,
all
>
~T
the three-dimensional
in
2
1
3
space defined by ait ), aV ), aV ). If we continue this procedure until
all the periods are exhausted, which must happen when the co-space
becomes /-dimensional,
if
not before, we shall have proved the
following theorem.
Theorem 4. For each periodic function V(x 1 .../, y l

of
.)
xf there is a system of periods co^, oV 2
oW with the
property that every period a> of the function F can be expressed in
the form
.
x1
The highest possible value of g, the number

to the number of variables/.
Definition 3.
tioned in theorem
of the periods, is equal
system of periods, possessing the property mena fundamental period system.
4, is called
We have represented all periods of F by means of a ^-dimensional

For this, of course, only the lattice points are essential, and
not the vectors joining them. If the system wW, &W
a>W were
replaced by another system, with the same number (g) of periods
lattice.
giving the same points of intersection, the new system of periods

oV 1 )', oV 2 )'.
coW would be equally suitable for the representation
.
74
of the periods of F.
systems
is
achieved
The coincidence of the lattice points in the two

and only if, the determinant of the rik s has the
if,
1.
This determinant represents the ratio of the cell volumes
two lattices. Thus we have
Theorem 5. All fundamental period systems of a function are
1.
connected by integral linear transformations with determinants
In the following we only consider functions for which the number
of periods in the fundamental system is equal to the number /of the
variables in which the periodicity holds. We consider therefore only
value
of the
functions of periodicity/.
xf
In place of the co-ordinate system x t
a
new
co-ordinate
system^
/-dimensional space
.
we
.
introduce in our
.
w f whose axes
,
are parallel to the vectors corresponding to a fundamental period

system for which these vectors form the units then the function F,
;
expressed as a function of the w's, has the fundamental period system

... 0)
(1, 0,
1,0...
(0,
(5)
In this case,
is
0)
(0, 0, 1
... 0)
(0, 0,
...
"
said to have the
1).
fundamental period 1."
This
leads us then to
Theorem 6.- By means of a linear transformation of the variables

which a function is periodic, it may be made to have the fundamental period 1.
in
We shall now see to what extent this co-ordinate system w w 2

l9
is still
First
arbitrary.
it is
by means
clear that
WzWz+ifj^w^Wz
wf
of a transformation
y lt?/ 2
.)
(6)
Wf^Wf+l/ljiWjWs
which each
Wf UHJz
wk s with the
.
.),
period 1 in each,
periodic in all the
xf) y t
will
not
the periodic properties of V(x l
be altered. The
.)
lattice points of the w-co-ordinate system pass to the lattice points
in
is
system by means of a simple displacement.

evident
that the given transformation is the only one
Further,
for which this transference from one set of intersections to the other
of the w-co-ordinate
it is
the result of a simple displacement. On passing, for example, from

a point in the w-space to an equivalent one, each w k increases by a
whole number. The wk must increase by the same whole number
is
when we carry out the similar transition
in the
fc
-space.
The
differ-
FEB10DIC AttD MtJLtlPLY PERIODIC MOTIONS
75
wk wk must
therefore have the same value for all equivalent

are
periodic in the w k and in the w k
points,
they
Now there are still other transformations for which the correlation
ences
i.e.
of the lattice points with values of the
wk
s will
be varied, but for which
with lattice point. To each of the fundamental period systems in the x k referred to in theorem 5, there
corresponds, for example, such a transformation these are the integ1ral homogeneous linear transformations with the determinant
Let us suppose that the most general transformation, which transforms the periodicity lattice into itself, be resolved into such a linear
lattice point will still coincide
one and also another transformation. This second transformation

must be of the form (6). The most general transformation is therefore
Theorem
All systems of variables, in which a function of

has
the fundamental period 1 are connected by transperiodicity /
7.
(7), where the r ik are whole numbers, the

of
which
has
the
determinant
1 and the
t are periodic in
system
the w k with the period I. 1
The function F may be written very simply with the help of the
w f It may be expressed as a Fourier series
variables w l
formations of the form
t/j
V(w l
(8)
w f )=
This theorem
2
'.-v
Cv.
TlT *'"
which the periodicity
Vfawi
is
preserved in the
T w '' f
'
"jiVi
'
'
f\
we seek a transformation
')
of the function
.
first
'
be proved analytically as follows
may
fc=4K^2
for
2n (TlWl
e'
*>
wf
yl
variables.
4K+1,
.)
= FKwa
iv
ff
$!
.)
we put
If
w>2
2/i
">/
=wk
',
then
F(w 1
wf
'
9
wr y
.)=-#(#! + 1, w 2
= y(w w^. ,wf1 y
.)-=F(?/' w> 2
that wk and wk differ by a whole number
yi
This means, however,
lt
4(î + 1 w t ...wf9 y l
4(î
is
where $k
is
w/f
+l
possible only
4(u>i
.)
'
..
.)=fk (u>i,
3> 9
We likewise conclude that

This, however,
periodic in
if
2/i
fk
js
.)=-/fc (Wi,
O f the form
wf fr .)=^r kl
the w with the period
.
1.
wr
yl
.).
76
which, for conciseness,
we
F(w)
(8')
the function
If
?-^W w
be multiplied by
and integrated over a
we get
unit cube of the w-space,
The
write
coefficients of the Fourier
expansion
therefore be obtained
may
the form
in
(\^(w)e~
(9)
>M ^dw
from the function F.

If
the function F(w)
is
real,
C Tl
T/
and C- r
T/
are conjugate
complex quantities.
14.
Separable Multiply Periodic Systems
Our next problem is to extend the results found for a system with
one degree of freedom to systems with several degrees of freedom.
In the case of absolutely general systems there is no object in
introducing angle and action variables, since these are associated
with the existence of periodic properties.
We
consider
first
the simple case in which the Hamiltonian func-
tion of the system resolves into a sum of terms, each of which contains only one pair of variables q k , p k
:
R=R
l (q 1 ,p 1 )+...+R f (q f Pf ).
The Hamilton- Jacob! equation is solved by separation
ables on putting
(1)
of the vari-
where the relation
Wl+
holds between the
pletely with that of

degree of freedom.
fc
It
is
seen that the motion corresponds com-
/ independent
We
consider
systems, each of which has one

the case where the variation
now
of each of the co-ordinates q k is periodic in time. The correct

generalisation of the earlier considerations is to define the action
variables
by
to express the function

(2)
S*.
in terms of q k
.-S.
and
J^,
and to put
77
massive particle is restrained by any set of

Example : Spatial Oscittator.
forces in a position of stable equilibrium (e.g. a
light atom in a molecule otherwise consisting of heavy, and therefore relatively immovable atoms). The
is then, for small
displacement, a positive definite quadratic
function of the displacement components. The axes of the co-ordinate system
(x 9 y, z) can always be chosen to lie along the principal axes of the ellipsoid
corresponding to this quadratic form. The Hamiltonian function is then
potential energy
H=
(3)
(px
4V+P*2 )+J^2 +~vy+>,2z
i
).
It has therefore the form of (1) above, so the motion

may be considered as the
resultant of the vibrations of three linear oscillators
along the co-ordinate axes.
We have then,
by
(9)
and
.)
(JO),
(4)
sin
Pz=
2nw z
where
The energy has the value

(
5)
W^JoH-VVl
The motion
is of
an altogether
different
v z .] z
type according to whether integral
linear relations
Tx vx
Vv 1-V=
between the v or not. We assume first that such relations do not exist.
can prove quite generally (see Appendix 1) that in such cases the path
exist
We
traverses a region of as
many dimensions as there are degrees of freedom it

approaches indefinitely close to every point in this region. In the case of the
spatial oscillator this region is a rectangular prism parallel to the axes having
;
sides of lengths
Vjx*>
A-V
*
vj;,
v
-*
vr
z
(spatial Lissajous-figure).
In order to see what special cases may arise when the v's are commensurable
with one another, we consider the simple case where vx v
This occurs when
y
the ellipsoid corresponding to the potential
energy possesses rotational
.
symmetry about the z-axis. The curve representing the path is situated then on
an elliptic cylinder enclosing the z-axis. Corresponding to a given motion we
no longer have uniquely determined values of J^ and J for we can rotate
v
the co-ordinate system arbitrarily about the z-axis, whereby the sides
perpen.
dicular to the z-axis of the rectangular prism

touching the path will be varied.
J z , on the other hand, remains uniquely determined as the height of the
elliptic cylinder
bility exists).
on which the path
Since the energy
is
is
situated
(if
no other fresh commensura-
78
W=(J.+
(6)
only the
sum Jx
If, finally, all
and none
system
-}-
Jy is determined by the motion.
may still
now
be arbitrarily rotated.
The energy
W=v(J x +Jv
(7)
the
is confined to an ellipse
uniquely determined, since the co-ordinate
three frequencies are equal, the motion
of the three J's are
is
!-.!,),
sum of the .J's will therefore remain unaltered by such a rotation.

now we ask what are the quantum conditions for such a system of
If
degrees of freedom, the obvious suggestion

(8)
In the ease of the
oscillator with
Jx
is
several
to put
J*=**A.
two equal frequencies vx ~v y the conditions
n x hj
Jv = ny h
are clearly meaningless. Lf, for instance, we have a motion, for which J x and
J y are integral multiples of h for any position of the x- and //-axes, we can
always rotate the co-ordinate system so that this property is destroyed. The
sum
,]
x -fF y ,
on the other hand, remains

.]
(i>)
integral, so that the condition
x +J v ^nh
significant. Since in the expression for the energy Ja and Jv occur

in this combination only, this quantum condition would not define the path
would still be
uniquely, but would
fix
the energy.
(10)
The example shows,
therefore, that only so

be prescribed as there are different periods.
three frequencies coincide there remains only the one condition
retains its significance.
quantum
If all
The condition
J Z =,A
conditions
many
may
J.+J^+J^nA
(11)
This again fixes the energy uniquely.

We shall now examine more closely the manner in which the action variables
alter when, in the case of vx
v y the co-ordinate system is rotated. Let the
action variables Jxt J y correspond to the rectangular co-ordinates x, y, and the
left.
action variables J 7 , J^ to the co-ordinates
x~x cos a y sin a

yxsin a -\-y cos a.
If
we express the barred
co-ordinates
and momenta occurring
m
in terms of those not barred (the
ordinates)
we
in
momenta transform
just like the co-
get
cos2
a+
2+v
(
sin8
a
2
pxp y -\-mca xy J
sin a cos a,
-|-
\w
px py
maAcy
79
sin a cos a.
j
The coefficients of cos 2 a and sin 2 a are clearly the magnitudes v,l x and vJ
The coefficients of sin a cos a we determine from the transformation equations
.
tf
(4)
and obtain
Jj= Jjc cos2 Ct Jy sm2 a ~~ ^ ^3 x')y cos WV~~ wy) s * n a eos a

J-= J^ sin 2 a-f J cos 2 a 2 V/J^J^ cos M^ t0y sin a cos a
The constants J^, J y
in our case wx ~w y is a constant since a = v
1~
>
tf
are
where,
thus transformed into Jj, Jy, which are also constants.
The transformation which transforms the angle and action variables, corresponding to a rectangular co-ordinate system, into those associated with another
?'
J'
rectangular co-ordinate system, is not one which transforms the angle and
action variables among themselves. In fact, the constant difference of the
angle variables appears in the transformation eq nations for the J. We shall
meet with a similar
state of affairs in the case of a second example,
and
later
quite generally in the case of degeneration.
that the Hamiltonian function does not consist of

terms
a sum of
depending on only one pair of variables q kp k but
that the Hamilton-Jacob! equation may be solved by separation of
the variables, i.e. on the assumption that
It
may happen
>
S=S
(11')
1(
Then
We
now suppose that each of the coa function of q k alone.

ordinates q k behaves in the same way as we assumed above ( 9) in
the case of systems of one degree of freedom, i.e. either that q k
is
and fro periodically in time, between two fixed limits

of
(case
libration), or that the corresponding p k is a periodic function
of q k (case of rotation). Since each integral
oscillates to
J*=#>*#fc
(12)
taken over a period q k

constant
momenta
is
constant,
we can
introduce the J^ here as
The function
in place of a t a 2 ....
depends
S may be expressed as a function of the y 's
then only on the J 's
and of the J 's. Instead of the q k s, the quantities w k conjugate to
fc
fc
fc
the J 's, will now be introduced

means of the equations
fc
as
(13)
they are related to the q k
^ as,
'
by
80
We will now prove that the variables w k> J k introduced in this way,
have similar properties to w and J for one degree of freedom, namely,
,
that the q k
are multiply periodic functions of the
wk s
with the
fundamental period system

(0, 1,
... 0)
... 0)
(0, 0, 1
... 0)
(0, 0,
...
(1, 0,
We
wish to find the change in
wk
1).
during a to-and-fro motion, or

when the other
in the course of one revolution, of the co-ordinate q h
co-ordinates remain unaltered.
Now, by
by integration
If
we
fix
1,
partial differentiation of equation (13)
so
w k by
This change will be
our attention on the functions qi(w

w f ), and increase
while the other w's remain unaltered, y goes through one
the remaining y's may also depend on w k but they return
.
fc
period
to the initial values without going through a complete period (if, for
example, qi went through a complete period Wi would increase by 1).
;
This proves the theorem stated above, concerning the periodic properties of the q k $ in the w k s.
It
that
may happen that a particular q does not depend on all the w k s,

is, it may not have the full periodicity/, but the system of all
the j's taken together depends of course on

In our treatment of the spatial
depended on one
oscillator, for
all
the
W A 'S.
example, each co-ordinate
only.
In every case q k
may
(U)
be expressed as a Fourier
?Jfc
=2 C W ^
series in the
form
2jrl(TW)
We
13, for the abbreviated notation adopted).
(see (8) and (8'),
obtain the w's as functions of the time from the canonical equations
OTT
(16)
tf*

Written as a function of
qk
81
=y\CW
T'Ky
(rf)^
where
0"')=T 1 V 1 +T 2
l>
T 8)=T 1 8 1 +T 2 8 2
(
so that q k
is
+
+
+Tf Vf
it Ls only periodic when, and

rational relations exist between the v's (for example
not in general periodic
only when, (/I)

when all the i/'s are equal). Periodicity of the motion signifies, therefore, that all individual periods (l/v k ) have a common multiple (l/i>,
say),
i.e.
that a relation
with integral T>"S, exists. This

rational relations between the v k
linear
homogeneous equations with

TIZV*
equivalent, however, to
is
&.
Conversely
(/I)
integral coefficients
determine the ratios of the i/ 's these ratios are rational,

fore possible to choose v so that
fc
(/I)
independent
it is
there-
Vk =fr k 'v,
the TJ/'S being integers. The Fourier representation of the co-ordinates q k assumes in this case the form
qh
= y\C w
e 2lTl[(T
>
T *' hT ' Ti/ h
'
T T
/ )lV
'
(T5)1
.
Here again the periodicity
will at once be recognised.

In the non-periodic case the motion is analogous to that which in
two dimensions is called a Lissajous-motion, the path being closed
only in the event of a rational relation between the v k a. We consider
the path in the w-space, confined to a standard unit cell of the period
13) by replacing every point on the actual path by the
lattice (see
equivalent point in the standard

relations between the v k n
cell.
If there are
no
linear integral
in the w-space
path
approaches innear
to
each
the
standard
cell
in
(as proved in
definitely
point
Appendix I). The representation of the g-space in the w-space is
continuous
this
so in this case the path in the ^-space approaches in-
an /-dimensional region.
such motions conditionally periodic.
definitely close to every point of
Astronomers
call
82
by J each time the co-ordinate q k
Since the function S increases
fc
traverses a period while the other

the function
gr's
remain unaltered, it follows that
S*=S-2>*J*
(16)
a multiply periodic function of the w's with the fundamental period

1.
For, if w k alters by 1, and the other w's remain the same, q k tra-
is
and the remaining
return to their original values,

without having completed a period, i.e. S increases by J and S*
remains unaltered.
verses one period
</'s
ft
S*
may
be regarded as the generator of a canonical transformaThe equation
tion instead of S.
is
in fact equivalent to
*"
-"
and
(H
this gives the transformation
3
*
?,
(17)
Pk ~
fyk
From
wo can deduce
a simple expression for the mean kinetic

energy in the case of iion-rektivistic mechanics. We have (cf. (8), 5)
If
this
we choose the time
interval
(t l9 t 2 )
suSiciently long,
it
follows
that
2T=
tz-
(18)
The
integrals
formulation of
Jk
(12) introduced here
quantum
appear to be suitable for the
conditions in the form
J k =n kh. By
defini-
tion, however, they are associated with a co-ordinate system (g, p)

in which the Hamilton-Jacobi equation is separable
it is therefore
;
essential that
we should next examine the
this co-ordinate
system
is
conditions under which
uniquely determined by the condition of
83
We
shall therefore see if there are point transformaseparability.

tions (i.e. transformations of the co-ordinates among themselves)
which transform the
set of variables in
which the Hamilton- Jacobi
separable into another such set.

equation
Let us suppose that there is a co-ordinate system, in which the
Hamilton-Jacobi equation of the motion under consideration is
is
We
suppose further, that no commensurabilities indeseparable.

"
"
identical
comof
initial
the
conditions, or, as we say,
pendent
mensurabilities, exist between the periods.
We can then choose
the
that the path does not close. If one variable

a
libration, the motion is confined between two (/!)q k performs
dimensional planes g^const., which are touched successively.
If,
initial conditions so
however, q k performs a rotation,

to a> k where w k is the corrc-
it
may
be confined to the region
spending period, by displacing

the parts of the path in the
intervals
back to the interval
(0,
The whole path
confined
then
the
to
is
interior
of
a> k ).
Fio.
7.
an
"
orientated in the direction of the
parallelepiped
The (/ l)-dimensional planes bounding the
co-ordinate axes.
"
/-dimensional
of the co-ordinate
parallelepiped have a significance independent
system.
By varying the initial conditions we can alter the dimensions of

the parallelepiped and so displace the invariable planes. It follows
that in this case (i.e. no identical commensurabilities) the directions
in the/-dimensional y-spacc which arc the axes of the co-ordinates in
which the Hamilton-Jacobi equation is separable have an absolute
individual variable can
significance, and that only the scale of each
be altered.
Hence
in the absence of identical commensurabilities all systems
of co-ordinates, in
connected by
which separation
of the variables
a transformation of the
is
possible, are
form
?*=/*(?*)
The associated momenta transform, by

equation
dfk
We thus have
(10),
7,
according to the
84
=fop k ~dq k +ft)g kdq k

J dq k
J'
integral on the right-hand side vanishes (on account of

the closed path of integration), and the first integral becomes
The second
$p kdq k
Thus the
integrals
J are
fc
really uniquely determined.
In the case of the spatial oscillator the path fills, in the general case, a
parallelepiped. In the absence, then, of identical commensurabilities, the rectangular co-ordinates, or functions of them, are the only separation variables,
and the integrals J x , J y9 and .7 z have an absolute significance.
If identical commensurabilities exist, the path does not occupy all
the space of the parallelepiped and the co-ordinate directions need
no longer possess an absolute significance. The J also need not be
fc
uniquely determined.
In the ease of the spatial oscillator with v x =v y9 we could rotate the coordinate system arbitrarily about the z-axis without destroying the property
of separation in x, y, z co-ordinates.
We obtained, in the various co-ordinate
Further, rectangular co-ordinates are not the
systems, different J^'s and J v 's.
only ones for which the oscillator may be treated by the separation method.
In order to show this and at the same time to give an example of the solution
Hamilton-Jacobi equation by separation, in a case where it does not
resolve additively (i.e. is not of the form (1)), we shall use cylindrical coordinates in treating the spatial oscillator for which v x v y v. The canonical
of the
transformation (12),
r cos
y= r sin
pr = p x cos
<j>
p^=
<f>
Z=Z
(/>
p x r sin
py
<f>
sin
<f>
p y r cos
<f>
Pz=Pz
transforms the Hamiltonian function into
Wo try
to solve the Hamilton-Jacobi equation
on the assumption that
S=S
Since
<f>
is
a cyclic co-ordinate,
s,=VIf
now we
terms dependent on
2
2
z
denote by
a> z a z , we get :
collect together the
constant, which
we
and put them equal to a

and, for the terms depending on
85
there remains
'
.drl
Two of
may be
the three action integrals
the auxiliary variable y^sin" 1
/ln
(
as in
J z = mu) z <j>(d z 2
On
substituting
2
jc,
the
9)
we
lind
nmo) z a z 2
z 2 }ldz
Jr =
(t)
form
integral takes the
first
m2
mco 2
jl
*")
evaluated at once ( J z by introducing
\-2bx
(h[
where
m co
2
This integral
(cf. (5)
in
ma> z
may be evaluated by the method given
Appendix
expressing a
in the Appendix.
,.
r- 2
and a z here
in terms of
"
J^
and J z we get
,
(O
W=v(2Jr
(20)
We get
II)
"'
By
l-J^)
^v t 3 t ,
for the energy
(i)~
==-,
vt
^.
It will bo seen from the equations (J9) that J r and J, have a completely
different
meaning from the quantities J x and J v derived by separation in

,
now
2jE times the angular

has
the
same
however,
meaning as before
z
also, the factor of v, namely 2.J r -f-'J,, has the same significance as the
former .1^+ J y (it is l/v times the energy of an oscillator for which J z is
In this case, therefore, a meaning could be attached to the quantum
zero).
rectangular co-ordinates
momentum about
J,, for example,
the z-axis.
is
conditions
2J7r -fJ
,]
The
Jr and J
restriction of
=wA
4>
individually
n z h.
by such conditions would, on the
other hand, lead to quantum motions altogether different from those arising
from the corresponding restriction of 3 X and J y in the case of a certain rect-
angular co-ordinate system.
We now
and the wr
We have
where
more
Jr J ..
consider
,
w^
closely the connection
between the
wx wy
,
J x Jv
,
86
is the component of angular momentum about the z- axis.

pressed here in terms of the angle and action variables by
2
(21
J ==
Here wx
tc
()
by
is
^J x J y sin 2ji(ivx -w y
On
a constant.
x and y are ex9,
we
find
).
the other hand

'>*
is
If
(!)),
<\
conjugated with J v
equal to the variable M;.--~,
<p
277
'1
he value of J r
is
found
from the equation

2.) r
and
is
Finally, the equation for

J
+J^J*-hV
given by
be obtained by calculating wr from J r and

motion and substituting for these quantities
wr may
of the equations of
^ with the hel]>
the values found above.
The transformation which connects the system ot variables wr

with
'r
the system wx w y J^Jy i no * ono which transforms the w's and the J's among
w y enters into tin* relations
themselves. In fact, the constant difference wx
between il^J r and Jg'I y Wo shall see that this is a characteristic of every
' /;
</>
>s
15 for definition of degenerate system).
degenerate system (see
15.
General Multiply Periodic Systems.

the Action Variables
Uniqueness of
Hitherto we have applied the quantum theory only to mechanical

systems whoso motion may be calculated by separation of the
variables. We proceed now to deal in a general manner with the
question of
variables
when
w k and
possible to introduce the angle and action

so admirably suited to the application of the
For this purpose it is necessary, in the first place,
it is
7c
quantum theory.
to fix the J's by suitable postulates so that only integral linear trans1 are possible
for it is only
formations with the determinant
;
in such cases that the

(1)
quantum
conditions
J*=%A
attached to them.
can have a meaning

Generalising our former considerations, we fix our attention on
mechanical systems x whose Hamiltonian functions H(j 1? p 1
)
do not involve the time explicitly. We assume further that it is
.
possible to find
new variables w k 3 k derived from the q k p k by means

,
1 The
following conditions according to J.
Rutherford-Bohr (Diss. Leyden), Haarlem, 1918,
Burgers, Hel Atoowmodel van

10.

a canonical transformation with the generator S
of
(q l9
Jj
87
.
qfy J f )
so that
k
=
^?*
o\
(2)
as
such a way as to
in
the following conditions
fulfil
(A) The configuration
be periodic in the w k s
which are uniquely deter-
of the
shall
system
with the fundamental period 1. The q k s,
mined by the configuration state of the system, shall be periodic
if for u,
functions of the w k s with the fundamental period 1
given
;
configuration of the system q k is indeterminate to the extent of an

integral multiple of some constant (27r, say), it is only the residue
of q k to the modulus of this constant whi^h is periodic.
In the
latter case there are also functions (e.g. sin q k )
the
w h9
in the strict sense of the
word
which are periodic in
13).
The Hamiltonian function transforms

depending only on the J 's.
(B)
into a function
W,
fc
It follows from this that the

and that the J 's are constant.
fc
wk
are linear functions of the time,
a periodicity lattice in the w-space, the

with sides 1.
Now
it
may
w f ) possess
the lattice being cubes
The functions q k (w l
cells of
be easily shown that the quantities J
fc
(apart from
being indeterminate to the extent of a linear integral transformation with the determinant
1) are not yet uniquely determined by
the two conditions (A) and (B).
simple canonical transformation, which does not violate the

conditions (A) and (B), is as follows
:
where the
c k s are constants.
The
J/)
arbitrariness in the choice of the
prevents the application of the quantum conditions (1) for, if the

Jfc's are determined as integral multiples of h, this will not in general
Cfc's
be the case for the J
fc
's.
We must therefore do away with this remain-
ing arbitrariness in the choice of the variables.
This
may be accom-
generally a property of the w's

previously to hold in the case of separable systems,
plished
(C)
by postulating
and
J's found
The function
J*
s*=s-2>*
k
which is the generator of our transformation
(qjcPk-+u>k3k) in
the form
(5)
shall be a periodic function of the w^'s with the period 1.

It is all the same here whether we regard S* as a function of q k
k9 since the g^'s are also periodic in the
k s.
k or of J/, and
and
be required in (C) that 1 shall be a fundamental period, (A)

be superfluous. For, if the q k n are calculated as functions of the
& and JYs from the second system of equations, they will be periodic
If it
will
wk
w k s with
Apart from this, it will be seen from the

same is true of the p k 'a.
system
We must now prove that the conditions (A), (B), and (C) really
suffice for the logical applications of quantum conditions in the form
we carry out the proof by finding the most general canonical
(1)
in the
the period
of equations that the
first
transformation
which
the conditions (A), (B), and (C).

of the transformation equations, viz. those
in terms of the w's and J's.
According to (A) the trans-
satisfies
We seek the iirst group

for
wk
formation must transform into
itself
the system of lattice points

1.
By (7), 13, the w k s
corresponding to the fundamental period

must transform as follows
:
(6)
Wfc
Here the system
of integers r fcz has the
periodic in the w k
with the period
in these also
w^s, periodic
form
determinant
1-
The
^'s are
and, written as functions of the

they may therefore be expressed in the
1,
The condition (B) introduces a fresh restriction. Considered as functions of the time, the w k s, as well as the w k 's, must be linear
from
;
(6) it follows
that
they vary at
all
just be
shown
are likewise linear functions of the time, but if

with the time they must be multiply periodic, as has
<^ fc
's
they must therefore be constant. This means, howexponent of the Fourier series, the only combinawhich can occur are such as make
ever, that, in the
tions of the
wk
independent
of
.+(7,8,)
t
and therefore
aw
J k ).
(identically in the
89
v k denotes here the derivative
-.
&Jfc
The case where
exist
tions
identical relations
between the frequencies will enter largely into our considerasystems for which such relations exist wejjshall call degenerate
systems, while the others
We shall deal also

values of the J A
we
shall refer to as non-degenerate.
with the case
i?i
which such relations exist only for certain

is then non- degenerate
the particu-
the mechanical system
motions in question, for which (TJ>)=(), we shall call accidentally degenerate,

whilst the motions of a degenerate system [(rv)=Q identically] are spoken of as
lar
intrinsically degenerate.
We
For these the trans-
consider
formation
first non-degenerate systems.

takes the form
(6)
(7)
Je
=
/
In order
now
to find the second group of transformation equations
of a non-degenerate
and
J's),
we
V(w l9 J l
write
.
system
down the
(i.e.
those for the J's in terms of the w'a
generator of the transformation
w J/) = 2 T J *^+^( J
f,
(7), viz.
J/)+W
w,),
kl
where
has the partial derivatives i/j k

transformation equations now becomes
(8)
In order to see
fc
if
-=
-^
The second group
2TJ,+/(
?!
Wf
of the
).
the transformation
(9)
actually leaves the conditions (A), (B), and (C) unaltered, or whether
we must still further restrict the number of permissible transformations,
we
resolve
them
into the three transformations
(10)
w^toi+hdi
(12)
&*=wto
It will be seen
from
this,
J/),
that the
's
1/1%
relations in order that the transformation
fc
=I*
J*=
*+/*(î
in (7)
must
may
fulfil
be canonical.
wf
).
certain differential
90
All three are canonical
sense of
to each
may
be assigned a generator in the
7.
The first transformation (10) does not conflict with (A) and (B).
That (C) likewise remains satisfied can be seen as follows If S(#, J)
and %(q, $) are the generators of transformations of the form (2),
transforming the q, p into w, J and into to, 3f respectively, then
:
since the
same
tiation, it
variables are maintained constant during the differenS .$ is independent of qk For S* j$* we
follows that
have then
k
from which it is seen that (C) is fulfilled.

It will be seen at once that (11) leaves (A) and (B) unviolated
we test as follows for the condition (C). For $*(j, in) and J$*(g, 5)
we have on the one hand
;
since the
(the
to's
same
variables are kept constant during the differentiation

to's by a linear transformation
are transformed into the
with a non-zero determinant) it follows that

depend on q. On the other hand
~~~
al*^_ _
&*
^*
docs not
^* ~
=v
and it follows from this that $* jj* is also independent of ffi and to.
In order that the complete transformation (9) may fulfil all three
conditions it is necessary and sufficient that this shall be the case
for (12).
For
$*(<?, to)
and
S*((/,
w)
we have
_ _
al*
as*
8q k
~T)if
8q k
thus
^*-S*=R(W!
Further, from (12)
thus
ibf).
91
remain valid for the transformation (12), R must be

periodic in the w k fk may therefore be represented by a Fourier
series without a constant term. If (B) is to remain valid,/*, must not
If (C) is to
depend on the time. From these two conditions it follows that fk

must vanish. Hence if / =0, (A), (B), and (C) remain unviolated.
We have proved by this that the most general transformation for
fc
the action variables
is
J*=2T
(13)
J,.
Ifc
If
the jys are now determined as integral multiples of
be true of the J k
Jfc/A
the same will
and conversely.
Although we have been guided

that
A,
must take
in our considerations
integral values,
we can
theorem proved in a form independent
of
by the idea
state the mechanical
any quantum theory
Uniqueness theorem for non-degenerate systems If we can introduce in a mechanical system variables w k and J so that the conditions
(A), (B), and (C) are satisfied, and if between the quantities
:
fc
no commensurability exists, then the J 's are determined uniquely,

apart from a homogeneous linear integral transformation with the
fc
determinant
1.
We proceed now to the treatment of degenerate systems.

If
between the
v k s there exist (/
s)
commensurability relations
2>*"*=0
(U)
we can
arrange, by means
of a canonical transformation satisfying

.
the conditions (A), (B), and (C), that/
s of
the frequencies
i>
= 0W
0J*
shall vanish
no relation of the
the new variables w k and J k once
and that between the remaining
type (14) shall

more, we have
exist.
If
we
call
e>
a=l, 2 ...
and the Hamiltonian function has the form
W(JJ.
s,
92
The w a 's and J a 's we call proper angle and action variables, the wp 's
and J p 's improper or degenerate variables the //;/ remain constant
during the motion. The number s of the independent frequencies v a
;
is
called the degree of periodicity of the system.
In the rase of accidental degeneration, the number of independent frequencies is less for certain motions than for the number of the whole system.
We call the former number the degree of periodicity of the motion under consideration.
We must now seek the most general transformation which violates

neither this division of the variables nor the conditions (A), (B), and
(C).
The
is
fc 'H)
first
now
group of transformation equations
(i.e.
that for the
fc
=2 T *i'^+^*K+i
'
f>
Ji
J /)'
The generator
is
therefore
t
.. J,)
'*/>
Ji
hi
where 1 F
is
periodic in the
equations then becomes
the derivative of
*
is
tf
The second group
of transformation
non-zero only
if
is
one of the numbers
./
In order that the division into non-degenerate and degenerate variables may persist, the w p 's must not depend on the w a 's or the w 's on
-
This means, however, that the r pfl 's vanish.

mation equations can then be written as follows
the
's.
ft
The
transfor-
w',=2'
a,
j8=l...
.p 9
(7=5
I
where
is
put equal to
the rpa vanish,

also
it follows,
<f>p
+1
=!...
Since the r kl are whole numbers
and
from the value of the determinant, that
We now divide the transformation (16) in two parts
93
.>
J>
(7
and
te fc
(18)
and show that the
J*-3 +/ (),
fcf
the condition (C) and that the second
0.
and ^(q,
J
and
q, ^->itr,
q, p-+w,
3) be the generators of the trans^

consider the function S
31.
before, let S(g, J)
formations
fc
fc
first satisfies
does this only for/a
As
from tho point of view of
S=%(ta,
its
We
dependence on
J), J),
-=
iu
%(ut,
and
i.e.
J,
we
write
J), 3(to, J))
and form
2*
r ^"*
from
(17),
the
two terms
first
A(S_)^_V U '^.
_(S-$)^0,
(19)'
'
We derive further
We have therefore
cancelling.
'
(B-9)-V
- T^ ^'-T
a?i
-J
?i
(20)
-*-?-.i-*-?>.
It follows
from
(19)
and
(20) that
S-*=T(to^ J)-Z toA.

(T
where
T has the same meaning as in (15).

k
We
shall
have therefore
this denotes, however, that (0) remains valid.
The condition that

(18)
is
(C) should be satisfied by the transformation

found as in the non-degenerate case, viz,
:
94
If (C)
in
and (B) are
satisfied,
fk (w)
is
a periodic function of the form
which only exponents containing wp alone may occur

always. It follows from this, however, that
conse-
quently r a
The most general permissible transformation of the non-degenerate

action variables is therefore
J.=ZvV
(21)
ft
The J
's,
on the other hand, need not transform
integrally.
Since the
condition (C) does not forbid the occurrence here of w l in the transformation equations of the Jp 's, it follows that from a system J in
p,
which
all
the Jp 's are integral multiples of A, a system J

p
be derived which does not possess this property
(cf.
may always
examples of
14).
We can state the result of our investigations independently of the

quantum theory as follows
If we can introduce in a mechanical system variables w k j k which
satisfy the conditions (A), (B), and (C), we can always arrange so
:
that certain of the partial derivatives
aw
s), are incommensurable while the remainnamely, the i> a 's (a=l
i/
vanish.
The J \s are then uniquely deterones
./)
ing
p (p=s+l
mined, apart from a homogeneous integral linear transformation
.
with the determinant ii. 1

We deduce still another consequence from the periodicity of S* as
the function
a function of q and w or J and w
;
increases by J k when w k increases by 1 and the other w's and

main constant. We can write this in the form
J's re-
Jfc
dw k
Jo
or
\Wj
=1 dw k y*Jo
fyi
-,
3k
J.
M. Burgers, who
complete proof.
refers to this
theorem in
his dissertation, does
not give a
95
(22)
This integral
may
be employed to ascertain
if
the quantum conditions or not, since all that

ledge of the p and q as functions of the w u 's.
16.
The Adiabatic Invariance
Quantum
a given motion fulfils

necessary is a know-
is
and the
Freedom
of the Action Variables
Conditions for Several Degrees of
As
in the case of one degree of freedom, the uniqueness of the

action variables is only one of the conditions necessary if the quan-
tum
conditions in the form
J a =n ah
are to have a definite meaning attached to them.
As a second condition we must require that the J a 's shall be constant
not only for an isolated system but also in the case of a system subject
to slowly varying influences, in accordance with the principles of
mechanics.
In fact the following principle applies in this case also
classical
The action
Ja
variables
are adiabatically invariant so long as they
remain in a region free from new degenerations.

We carry out the proof (after J. M. Burgers) exactly as we did
in the case of one degree of freedom. 1 We imagine the canonical
transformation
as*
applied to the variables q k p k satisfying the canonical equations

,
an
8H
"-iff
*^;
so that, for constant a, the variables q k p k are transformed into the

angle and action variables w k , J k
By (1), 7, is transformed to
,
as*
H = H+ ir
Thus the transformed canonical equations can be written
1
free
The proof
of the adiabatic invariance of the J's given here is not altogether

of difficulties due to the appearance of accidentally
from objection on account
degenerate motions in the course of the adiabatic change.

given by M. v. Laue, Ann. d. Physik, vol. Ixxi, p. 619, 1925.
A strict proof
has been
96
W= 8R
8 /8S*\
___
~~8w ~dw
s
Since
H depends only on the J k

T
'$, it
=_
a
k
\df/'
follows that
-8w k \
dt
i'
8w k \ da
In the differentiation with respect to t and a, S* is to be regarded as

a function of q k w k and t or a. Now the variation of J in the time
,
interval (t^
fc
t 2 ) is
and on account
of the supposed slow alteration of a, independently of

the
the period of
system, a can be put before the integral sign. We
will now show that
tk
a
of the order of
is
S*
is
magnitude
d(t 2
a periodic function of the
grand of
(1) is
a ) (cf.
wk
10).
f'S*
so also
is
--
and the
inte-
da
a Fourier series
without a constant term, so that the integral to be evaluated takes

the form
where AT
v,
and S are functions
of the J's
and
of a.
We
integrand in the neighbourhood of a certain value of

denote by =0 as in 10, and obtain
2 'A
TO
e'-'TiKT^M
(r
develop the
t,
which we
)]
(2)
the notation being similar to that used in (4),

10.
Consider
this expansion carried out at the beginning of the interval (^, t 2 )
arid the integral taken from t l to such a point that the integral
97
of the first term vanishes.
This is always possible, since the indefinite

integral of the first term is a multiply periodic function, and in
intervals of the order of magnitude 1 /(TV O ) passes continually through
zero.
The
integral of the second
tude dT or aT 2
term
is
of the order of
We imagine now a new expansion (2)
magni-
carried out at
the beginning of the remaining interval and the integral again taken
so far that the first term vanishes. This process we suppose con-
tinued until finally there remains an interval over which the integral
of the first term has a non-zero value. It will be seen that, if none
of the (rv)'s vanish on the path of integration, the complete integral
of the order of magnitude d(t 2 t t ).
is
In the case where an identical relation

for a certain value of
J's) (VT) ^0 exists
so that the
are incommensurable
(i.e.
a relation valid for
the w's and J\s
all
may be chosen
and the
v 's equal to
(cf. (14),
p
then
Constant
exponents ((rv)=0)
appear in S*, but they in15).
volve the w p 's only the terms in question disappear, therefore, on
differentiating with respect to w a consequently the J a 's remain ini/
's
variant at such places of degeneration

to hold for the J 's.
this
cannot be said generally
In addition to those cases where (TV) is identically zero, it may

happen that (TV) is zero only for the particular values of 3 k under
consideration
tion,"
in the latter case
we speak
and under such circumstances the
of
J's
"
accidental degenera-
need not be invariant
unless, in the expansion (2) of the integrand of (1) for the different
J fc 's, the term r0 with the corresponding exponent (TW) occurs in S
with zero amplitude.

It follows then that
must exclude
all
if the J^'s are to be adiabatically invariant we

cases for which an accidental commensurability
for the values of J under considera(i.e. one which holds only

occur conjointly in the form (TV) in
which
between
tion)
frequencies
the exponent of a term of the Fourier series for S*.
exists
As an example
of the adiabatic invariance of
the case where the mechanical system
an action variable we consider
invariant with respect to a rotation

are cylindrical co-ordinates, the angle
be introduced as co-ordinates
x may
is
about an axis fixed in space. If (/*, <, z)

of rotation <^ and the differences ^j.
instead of the individual
6) the
fa is then a cyclic variable, and (cf.
momentum conjugated with it is the angular momentum of the system about
the z-axis. The principle of the conservation of angular momentum about an
axis is also valid when the expression for the potential energy contains the time
explicitly, provided only that the invariance with respect to a rotation about
<
<f>
the axis persists identically in time. If the field of force of rotational symmetry
be strengthened or weakened, the angular momentum about the z-axis remains
invariant, and we have a special case of the principle of the adiabatic invariance
of the action variables,
98
In order to see what may happen in the case of a passage of the system
through a degenerate state, we consider once again the spatial oscillator. We
suppose that the directions of the principal axes of the potential energy ellipsoid
as well as the magnitudes of the three frequencies are functions of a parameter a, which can be varied arbitrarily in time. If now for a certain value
of a no commensurability exists between the freq uencies, the J's will be adiabatic
invariants. If, however, for a certain value of a we have degeneration, e.g.
vv
no longer be the case, though certainly there are special variawhich the J's do remain invariant. If, for instance, the directions of
v y i this will
tions for
the principal axes are left unaltered and only the frequencies varied, the coordinates behave as independent linear oscillators, and the J's are adiabatic
invariants for each individually. As an example of an adiabatic variation in
which the J's do not remain invariant in the ca>se of degeneration, we consider
the following. We allow the original potential energy ellipsoid with three
unequal axes to pass over into an ellipsoid of rotation, keeping the axes fixed ;
without varying the axis of rotation we now allow the axes of the ellipsoid
again to become all unequal, but with the other two axes turned through a
angle with respect to the original ones. In the instant of degeneration
the projection of the motion in a plane perpendicular to the axis of rotation is
an ellipse. The limiting values of the J's which are correlated with the J values
finite
before and after the degeneration are determined by the amplitudes of this
motion in the directions of the principal axes of the potential energy
it will be seen at once that these values are different for different
ellipsoid
elliptic
directions of the axes.
The uniqueness of the J a 's (in the sense of 15), together with their
adiabatic invariance, strongly suggests the following generalisation
of the quantum condition for one degree of freedom
:
In a mechanical system which satisfies the conditions (A), (B), and

(C)of 15,lettheit; A.'sandJ sbechosensothatthey a s(a=:l,2
.s)
>
A:
are incommensurable
and the
's
(p^s+1
/) are zero
(it
may be
that s=f). The stationary states of this system will be defined

,
the conditions *
T
n
rt
Ja
(tt=l, 2
a/i.
.
=n
is
Since the Hamiltonian function depends only on the Ja 's

determined uniquely by the quantum numbers n a
its
by
x
s).
value
To this is added,
condition
as the second
quantum principle, Bohr's frequency
W=sW
-W.
1
The first generalisation of the quantum conditions for systems of more than
one degree of freedom was given by M. Planck ( Verh. d. Dtsch. Phys. Ges., vol. xvii,
pp. 407 and 438, 1915), W. Wilson (Phil. Mag., vol. xxix, p. 795, 1915), and A.
Sommerfeld (Sitzungsber. d. K. Bay. Akad. t p. 425, 1915). All three start out
by equating the action variables to integral multiples of h. The general case
of multiply periodic systems was dealt with by K. Schwa rzschild (Sitzungsber. d.
Preuss. Akad., p. 548, 1916), and tho conception of degeneration together with
the restriction of the quantum conditions to the non-degenerate J's was first made
clear by him.
The unique determination of the J's through our conditions ( 15)
is given
by J. M. Burgers, Het Atoommodel ran Rutherford- Bohr (Diss. Leyden,
1918).
We
99
now collect together once more the fundamental ideas

the
underlying
quantum mechanics as hitherto developed the totality
will
of the motions (supposed multiply periodic) of a given model are to be

calculated according to the principles of classical mechanics (neglecta discrete number of motions will be
ing the radiation damping)
;
continuum by means of the quantum conditions.

The energies of these selected states of motion will be the actual energy
values of the system, measurable by electron impact, and the energy
selected
from
this
differences will be connected with the actual light frequencies emitted

by Bohr's frequency condition. Apart from the frequency the ob-
servable qualities of the emitted light comprise the intensity, phase,

state of polarisation
with regard to these the theory gives
and
approximate results only ( 17). This completes the properties of

the motion of atomic systems which are capable of observation. Our
calculation prescribes still other properties, however, namely, frequencies of rotation and distances of separation in short, the progress
motion in time. It appears that these quantities are not in
1
This leads us, then, to the congeneral amenable to observation.
;
of the
method is, for the time being, only a formal scheme

of calculation, enabling us, in certain cases, to replace true quantum
principles, which are as yet unknown, by calculations on a classical
clusion that our
basis. We must require of these true principles that they shall

contain relations between observable quantities only, i.e. energies,
light frequencies, intensities,
and phases. 2 So long as these
principles
unknown we must always be prepared for the failure of our

one of our main problems will be to deterpresent quantum rules
are
mine, by comparison with observation, the limits within which these

rules are valid.
The Correspondence Principle

of Freedom
17.
As
in
11,
we must now
investigate to
for Several Degrees
what extent the
classical
theory may be regarded as a limiting case of the quantum theory.

In this limiting case the discrete energy steps run together into the
We
show further that a relation

continuum of the classical theory.
similar to that holding in the case of one degree of freedom exists
between the
When
classical
and quantum
frequencies.
the classical radiation damping
is
neglected, the electric
1
Measurements of the radii of atoms and the like do not give a closer approximation to reality than, say, the agreement between rotation frequencies and light
frequencies.
2
This idea forms the starting-point of the new quantum mechanics. See W.
Heisenberg, Zeit. f. Phya., vol. xxxiii, p. 879, 1925.
100
moment of the atomic system may be represented by

of the
D^^^^ZO^K"*
(i)
The components
KT5)j
C T are complex quantities since the

components of CT turn into the conju-
of the vectors
of p are real, the
components
gate complex quantities when the signs
including in the constant the
By
a Fourier series
form
of all the T fc 's are reversed.
terms in
it
pj
may
be arranged
that only the non-vanishing (and incommensurable) frequencies va

occur in the exponent (see (14'), 15, for significance of suffixes a
and
p).
Now the quantum frequency
associated with a transition in which
way
r s corresponds, in an analogous
by r l
of
of
one
to the case
freedom, to the overtone of frequency
degree
The
relation
the quantum numbers
quency
is
between
alter
this classical frequency and the quantum frebetween a differential coefficient and
in this case also that
a difference quotient.
We consider a fixed point J a in the J a-space and
all
the straight
lines
J.=J.-TaA,
going out from this point, the directions of which may be pictured
as lines joining J a with the angular points of a cubic lattice (of arbitrary
mesh magnitude) surrounding
quency
may
The
this point.
then be written in the form
classical fre-
The quantum frequency may be written
in the
form
--
(3)
In order to describe the relation between (2) and (3) we imagine the
above-defined grating chosen so that the side of the cube is equal to
is then the decrease in the energy in going from the
h, v
grating
J
rji, expressed as a multiple of the
point a to the grating'point J a
mesh magnitude h. The classical frequency is obtained when the mesh

magnitude h
is
made
infinitely small.
also be looked upon as a mean value

between
the grating points J a and Ja
frequency
rji
The quantum frequency may

of the classical
1
The
signs arc chosen so that emission occurs
when
all
the r a 's are positive.

for a finite h,
frequency.
If
as a certain
i.e.
orbits of the
quantum
101
mean value between the initial and final
transition, associated
with radiation of that
We have in fact *
the alterations r k of the
quantum numbers
are small in
com-
parison with the numbers themselves, the expressions (3) and (2)
differ very little from one another.
As in the case of one degree of freedom, the correspondence prin-
be employed for the approximate determination of the

and states of polarisation.
If the alterations r k of the quantum numbers are small in comparison with the numbers themselves, the Fourier coefficients C T for
the initial and final states differ by a relatively small amount. On
the basis of the correspondence principle we must now lay down the
following requirement For large values and small variations of the
quantum numbers, the light wave corresponding to the quantum
transition T I
ra is approximately the same as that which would
ciple may
intensities
be sent out by a
classical radiator
with electric
moment
C^fr-o
This determines approximately the intensity and state of polarisation of the wave. The same quantities C r determine also the probabilities of transitions
between the stationary
states.
quantum numbers are of the same order

of magnitude as the numbers themselves, it seems likely that the
amplitudes arc determined by a mean value of C T between the initial
and final states. How this mean value is to be determined is still
an open question. 2 It can be answered only when certain components
it may be assumed that the
of the classical C T are identically zero
If
the alterations of the
corresponding oscillation is also absent in the quantum theory.

These considerations can be applied in practice to the determination of the polarisation only if, during the process, at least one
direction in space is kept fixed for all atoms by external conditions,
e.g. an external field. In other cases the orientations of the atoms
irregular and no polarisation could be established. If, for
example, a certain CT had the same direction for all atoms, then
to this would correspond a linearly polarised light wave with the
would be
Comp. H. A. Kramers,
Intensities of Spectral Lines (Diss.
Ley den), Copenhagen,
1919.
This question is now answered by the new quantum mechanics founded by

Heisenberg (loc. cit.) and developed by Born, Jordan, Dirac, Schrodinger, and others.
2
102
distribution of intensity given

directions in space.
by the
classical
theory for different
Of special importance for the application of the quantum conditions and of the correspondence principle is the case in which the
Hamiltonian function is not changed by the rotation as a whole of
an atomic system about a fixed direction in space. If we introduce
as co-ordinates the azimuth <f>=qf of one of the particles of the
system together with the differences of the azimuths of the other
and other magnitudes depending only on the relaparticles from
<j>,
tive position of the particles of the system with respect to the fixed
direction in space, </> will be a cyclic variable and the momentum
conjugated to
it is,
by
6,
the angular
of the
p^
system
flS
On
parallel to the fixed direction.
momentum
account of the constancy of
U</)
the function S, which transforms the q k and their

angle and action variables, has the form
It follows
from
momentum p k into
this that
8F
0S
0s
0F
If
now
qtfz
88
gy_ a be kept fixed
and
<f>
allowed to increase by
the whole system be rotated through 2-rr), the w k a must

change by whole numbers (for the q k s are periodic in the w k s with
the period 1)
for this to be the case the derivatives of F must be
2ir (i.e. if
whole numbers and
has the form
F=r 1J 1 +
+T/J/+C.
By means of a suitable integral transformation with the

minant
1 this may always be brought to the form
so that
deter-

from
It follows
this that
"*=<&*(li
and by solving
f
TA^W!
JL_^
so that
we can
?/-i>
Ji
w f-ii
Ji
w^J must be periodic
S= 1 ty+Sfo
(7)
(*=1
J/-i>- Jj
(&
-/-I)
./I)
write also
S=v(J,+c)+p(J,+c)+<FK
47T
Since S
J/-i J,)
for the q k
?&
6)
103
The angular momentum
in
w^
7/-i,
it
v_!, Ji
follows that
Ji
J/-L
J,).
c=0 and
so
J,_i, J,)-
in the direction of our fixed axis
is
conse-
quently
_as_
*~^~~2i'
*'
no degeneration then we must put
If there is
In every system for which the potential energy is inIn words

variant with respect to a rotation about an axis fixed in space, the
component of the angular momentum about the axis multiplied by
:
2rr is
an action
variable.
If the
energy depends essentially on this
to be quantised.
quantity,
Since the functions <D/C in (5) depend only on the relative positions
of the particles of the system with respect to one another and to
it is
the fixed axis, these relative positions will be determined also by

w/_i, while Wf fixes the absolute position of the system.
According to (6), 27rw/ can be regarded as the mean value of the
wl
azimuth of the arbitrarily selected particle of the system over the

"
"
motions of the relative angle variables w t
M/-I. The motions
can therefore be considered as a multiply periodic relative one on
which is superposed a uniform precession about the fixed axis. If
H, regarded as a function of the J^., does not depend on J this precession is zero
the system is then degenerate.
We consider first the case where the system moves under the action
<f>
104
of internal forces only. Every fixed direction in space can then be

regarded as the axis of a cyclic azimuth. The energy does not depend
on the individual components of the resultant angular momentum,
but only on the sum of their squares,

resultant angular
momentum.
If
i.e.
on the magnitude of the
the direction of the angular mo-
mentum
is
be chosen as axis, the corresponding azimuth
and w^ non-degenerate. The resultant angular momentum p is
fore determined by a quantum condition of the form
iff
cyclic
there-
27rp=J^jA.
(8)
If
we
our attention on a second arbitrary axis fixed in space,

the associated action
be a cyclic azimuth <j> about this
fix
there will
variable J =27rp^ does not occur, however, in the energy function in

because the energy of the system cannot depend on a
addition to
component
able
J^,
of momentum in
w^ conjugated to
is
an arbitrary direction. The angle varitherefore degenerate, and J may riot be
The significance of w^ will be recognised from the general

of
a
cyclic angle variable, that it is equal to the mean value
property
of the azimuth of an arbitrary point of the system taken over the
quantised.
axis,
w^ is thus a constant angle which can
be chosen equal to the azimuth of the axis of the resultant angular
momentum about a plane through the fixed ^-axis.
motions relative to the
We now
jected to a
consider the case where the mechanical system is subhomogeneous external (electric or magnetic) field. The
azimuth
of a particle of the
</>
then a cyclic variable

have the quantum condition
field is
system about an axis parallel to the

H will depend on J^, and we
in general
(9)
27rp,=J,=wA.
For an arbitrary external field, on the other hand, the resultant
angular momentum p is not in general an integral of the equations
of motion and cannot therefore be quantised, but it may happen,
in special cases, that p is constant and is an action variable. The
relations (8) and (9) will then be true at the same time
but p^ is
the projection of p in the direction of the field and, if a denotes the
angle between the angular momentum and the direction of the field,
we have
;
^.
cosa=
(10)
P
This angle
J*
therefore not only constant (regular precession of the

resultant angular momentum about the direction of the field), but
is
is
also restricted
by the quantum condition to
discrete values.
One
PERIODIC AND MULTIPLY PERIODIC MOTIONSspeaks, in this case, of
take only the values
"
105
Since by (10)
can
spatial quantisation."
it
follows
that
for
there
j,
every j
j+l,...j,
all 2j +1 possible orientations of the angular momentum. This

describes a cone of constant angle a about the direction of the field
are in
with the processional velocity
This regular precession
We
initial conditions.
is,
in general, possible only for certain
show later (by the method of secular

for weak fields, the spatial quantisation
shall
18) that,
perturbations,
holds in general for every motion
the only exceptions to this are
certain cases of double degeneration (e.g. hydrogen atom in an
;
electric field,
35).
cf.
Certain predictions regarding the polarisation of the emitted light

and the transition possibilities may now be made with the help of
the correspondence principle.

If z is
ponents
an axis
of
symmetry
of the electric
fixed in space,
moment
$x $ y
,
form of a complex quantity and write
we combine
the com-
perpendicular to this, in the
(4=1,
2,
...
n).
Pi=2- e ***
k
If r k s are
the distances from the axis and
them being
<f>),
<
fc
's
the azimuths (one of
then
Now
the bracketed expression (r k e ^-^) like the z k depends only

on the #!,... y/_i substituting for these the values (6) we have
,
T/
The integer r can therefore assume only the value

components of the electric moment and the value
the x- and yin the case of the
1 in
According to the correspondence principle, the corresponding quantum number can alter only by 1 or 0. (This holds, of
course, only if J is to be quantised at all, i.e. provided there is no
z-component.
degeneration.)
1
The change
of
corresponds to a right- or
A. fcommerfeld, Phys. Zeitschr., vol. xvii, p. 491, 1916
Ann.
d.
left-
Physik, vol.
li,
p. 1, 1916.
2
The sign of ris meaningless, since in the Fourier expansion

as well as T.
T always occurs
106
handed rotation of the
electric
moment about the
axis of
symmetry,
and, therefore, to right- or left-handed circularly polarised light.

Since the angular momentum of the system increases when the quantum number changes by +1, that of the light therefore decreases, so
+1 in J^ the light is negatively circularly

for
emission
and
positively circularly polarised for absorppolarised
1
1 in J the reverse holds.
tion ; for the transition
Corresponding
that for this transition of
(/>
to the transition without change of angular momentum, we have

2
If the motion of
light polarised parallel to the axis of symmetry.
each point of the system is confined to a plane perpendicular to the
axis of
symmetry then (except
ioi r l
rf_ 1 =0)
-,-=
a transition without change of angular
momentum
does not then
occur.
We
now
the case of a system which is subject to internal

The above considerations are then applicable to the
consider
forces only.
axis of the resultant angular
angle denoted above

applies.
since the
momentum, where, in place of <, the

appears and the quantum condition (8)
by
The polarisation of the light cannot be observed, however,
atoms or molecules of a gas have all possible orientations.
ifj
the particles of the system move

in planes perpendicular to the axis, is of frequent occurrence, e.g. in
the case of the two-body problem (atom with one electron) and in
The case mentioned above, where
all
that of the rigid rotator (dumb-bell model of the molecule)

transition j->j
is
the
then impossible.
We consider further the case in which the system is subject to the

action of an external homogeneous field and spatial quantisation
is
approximately true for weak fields). The alterations
exists (which
of
and the polarisation
Aj
We
of the light are then subject to the rules
easy to see that the transition possibilities

1, 0, +1, which are valid for a free system, remain true for j.
introduced so that the
imagine a co-ordinate system f 77,
derived above.
It
is
in the direction of the angular momentum,

perpendicular to the direction of the field. In this
-axis
is
ordinates the electric

1
moment may
and the
ij-axis
system of cobe expressed in the form
Hubinowicz (Phyaikal. Zeitechr., vol. xix, pp. 441 and 456, 1918) used the
between polarisation and angular momentum (about the same time as the
general correspondence principle was given by Bohr) in order to arrive at the
selection principle for the alteration of quantum numbers.
2
In optics, such light would be said to be polarised perpendicular to the zdirection, since the plane of polarisation is taken conventionally as the plane of
oscillation of the magnetic vector.
relation
107
which only the angle variables of the relative motion w t

w/-i
(not w^ and w^) occur in the summations. The co-ordinates f rj,
are connected with those of the fixed system x, y z by the relations
in
x+iy=e
2irlw
<l>(g
z=
cos a
sin
sin a-f
cos a
a+i^)
;
which express the fact that the -axis makes a constant angle a with
the z-axis, and describes a regular precession w^=vj about it. The
same transformation formulae hold also

vector p in the two co-ordinate systems.
for the
substituted for p f p o p^, it

occur only with the factors T
ables WQ and
,
components of the
the Fourier series (11) be

will be seen at once that the angle variIf
=l
in
r^ 0, J^l,
w^
the exponents of the Fourier series for PJ,. and p v and in p z with the
1 only. The quantum number j can therefore
factors r =0
r^=0,
;
or
change only by
1.
Method
18.
of Secular Perturbations
A multiply periodic degenerate system may frequently be changed

into a non-degenerate one by means of slight influences or variation
of the conditions.
shall consider, in particular, the simple case
We
where the Hamiltonian function involves a parameter A and the

system is degenerate for A=0. We imagine the energy function
of A
for sufficiently small values of A

;
powers
expanded
off
after
this
series
the
term linear in A and write
break
in
H^Ho+AH!.
(1)
To
we can
approximation then each perturbation of the unperturbed

of
may be taken account
system, whose Hamiltonian function is
"
"
AHj.
by the addition of an appropriate
perturbation function
The effect of the perturbation function on the motion, when the
is not degenerate, will be
system whose Hamiltonian function is
this
examined
later
here
we
only the case where
shall consider
is
We
degenerate.
suppose the problem of the unperturbed system
solved and angle and action variables w kQ 3 kQ introduced by a canon,
ical substitution
on account
of the degeneration,
will
depend
15,
s) (see (14'),
only on the proper action variables J a (a=l, 2
for the significance of suffixes a, p).
x will be a function of all the
.
w k*'a
(2)
and J
fc
's,
thus
108
We obtain an approximate solution of the " perturbation problem "

by a method which will here be based on an intuitive line of argument it will be established mathematically later in a more general
;
context (Ch. 4, 43).

In the undisturbed motion the w p
The
able with the time.
the
's
will also
()
's
are constant
and the w a
's
vari-
be that
effect of a small perturbation will
be variable in time, but in such a manner that their
rates of change will be small, i.e. that they vanish with A. Since now
the co-ordinates q k p k are periodic functions of all the w k 's with the
,
period 1, it follows that, during the time in which the wp

a given amount, the system will have traversed a large
vary by
's
number
of
periods (rotations or libratioiis) of the w a 's. The coupling between the

motions of the w a 's and the wp 's may therefore be represented approximately by taking the mean value of the energy function over the
unperturbed motion of the
wa
(2)
then becomes
H-HO^+AH^ %
(3)
<>,
JP
).
In this expression the w a 's do not appear the J a 's are therefore
constant during the perturbed motion, and appear as parameters
only the only variables are the w p 's and J 's. These satisfy the
;
canonical equations
The only solutions which are of importance from the point of view of
the qiiantum theory are those of a multiply periodic nature. We
assume, therefore, that the perturbed motion has a principal function
of the
form
(5)
where F is a periodic function of the wp 's with the fundamental period

1, and such that the canonical transformation with the generator S,
viz.
W.=.
8V
c)F
(6)
W+*r
J/^+aT,
H into a function of the J

Hô; ^-VHW^J,,).
transforms the function

(7)
The portion
= Ja
of
S depending on
w>
Jp
viz.
fc
's
alone
109
a=l
satisfies
the Hamilton-Jacobi partial differential equation
The variations of w p J p are determined, therefore, from the mean of

the perturbation function just as the original co-ordinates of a system
are from the total energy function.
To
this
approximation the solution takes the form
-const.
Wa
fi
wp =
J =const.
p
where
" tt
~_sn
We see, therefore, that the rates of variation of the w

compared
with those of the
mechanics the name
"
w a 's and
\s
p
arc in fact small
vanish for A=0.
secular perturbations
"
In
celestial
has been introduced
for such slow motions.
It will be seen
that the original co-ordinates q and p of

periodic functions of the new angle variables w as
from
(6)
the system are now

well as of the old angle variables
wa
For the motions represented by equation

tion. rotation, or limitation
practically only
variables w? or
9
That
is
if
if
may
exception of one, are cyclic
wp
(8) also,
cases of libra-
This problem
soluble
is
the differential equation (8) is separable in the

it is possible to find other separation variables.
the case, for example,
one variable
occur.
appears,
i.e.
if all
the variables
wp
or
all
with the
the simplest case is that in which only

when the unperturbed system is simply
degenerate.
Further,
it
may happen
that the problem defined by

wp '&, in which case these w
degenerate in respect to certain
H
p
is
also
remain
constant during the motion. By the addition of a further perturba9

tion function these w p s can, of course, become secularly variable.
The calculation of the mean value of the perturbation function H!
frequently simplified by employing the original variables q, p instead of the angle variables, and averaging with respect to the time.
The orbital constants of the unperturbed motion, which occur in the
is
110
mean value
have then to be replaced subsequently by the de19

generate angle variables wp and by the action variables J^.
In the case of a system subject to internal forces only, the azimuth,
.
about any straight line fixed in space, of a plane passing through the
axis of the resultant angular momentum and this straight line is a
degenerate co-ordinate and is constant. If now a weak external
homogeneous field, having the direction of this straight line, acts on
this system, the mean value of the perturbation function AH^ cannot
depend on this azimuth. If now there is no other degenerate vari-
able of the unperturbed system which could be secularly varied by

means of the perturbation function (as is, for example, the case for a
37), then the only secular
hydrogen atom in an electric field, cf.
motion induced by the external field is a precession of the resultant
angular momentum about the direction of the field with the frequency
We
have then an approximate realisation of the case of spatial quanwith in the foregoing paragraph. The exact motion
it
differs from that described by small superimposed oscillations
"
is a
pseudo-regular precession."
tisation, dealt
19.
Quantum Theory
of the
Top and Application
to Molecular Models
We
have already examined (in 12) the motion of diatomic moleu

we considered as rotators." We shall deal now with
which
cules,
the general case of molecules containing several atoms, regarded, to a
first
approximation, as rigid bodies.
The case
of diatomic molecules,
mentioned above (and generally of molecules for which all the atoms
lie on a straight line), will then appear as a limiting case, and we shall
obtain, at the same time, a more rigorous foundation for our previous
results.
The conception of molecules as rigid bodies must, of course, be

founded on the electron theory
for, actually, the molecule is a
of
several
nuclei and a large number
made
up
complicated system
*
of electrons. It can in fact be shown that the nuclei move, to a
close approximation, like a rigid system, but the resultant angular
momentum of the molecules will not be identical with the angular
;
momentum
of the nuclear motion, because the electron
possesses, relatively to the nuclei,

1
system itself
an angular momentum of the same
M. Born and W. Heisenberg, Ann.
d.
Physik, vol. Ixxiv, p.
1,
1924.
111
order of magnitude. We arrive, therefore, following Kramers and

1
Pauli, at the conclusion that the adequate molecular model is not
simply a top, but a rigid body, in which
is situated a
fly-wheel with
shall consider then, in this paragraph, the theory
fixed bearings.
of this top provided with a fly-wheel.
We
Let the top, including the mass of the fly-wheel (which we take as
symmetrical about an axis, so that the mass distribution is not
altered by its rotation), have the principal moments of inertia A,, A
A a the axes of which shall be, at the same time, the axes of a colet A be the moment of
ordinate system (x, ?/, z) fixed in the top
inertia of the fly-wheel. Let a be the unit vector in the direction of
tf
the angle of rotation of the fly-wheel
the axis of the fly-wheel,
about its axis, and ô> its angular velocity. As before, we note
by d the vector of the angular velocity of the whole top, and to
define the position of the top relative to axes fixed in space, we
again employ the Eulerian angles 6, ^, i/j (0 and i/t pole distance and
azimuth
axis).
A -axis,
the angle between nodal line and the A^between the derivatives of 0, <, and the comd have been given previously (in (2), 6). Let D be the
of the
The
(f>
relations
iff
ponents of
vector of the resultant angular momentum of the body.
The components of the total angular momentum are made up of
the components due to the top alone and those of the fly-wheel
:
D =A
(1)
lf
The angular momentum
ir
lf
+A
of the fly-wheel
about
its
axis
is
Q=A(oH-(da)).
(2)
The four equations
motion are obtained by applying the principle

momentum. In the first place, the
total angular momentum must remain constant in magnitude, and
of
of the conservation of angular

in a direction fixed in space
this gives the Eulerian equations
D=[D,
d].
momentum
of the fly-wheel can be changed

with
the
interaction
only through
body of the top resulting in a
of
its
the
axis
alteration is therefore perpenin
direction
;
change
Secondly, the angular
dicular to the axis, so that

is
constant
1
W.
H. A. Kramers,
Pauli,
jr.,
its
component
in the direction of the axis
i.e.
Zeitschr. f. Physik, vol. xiii, p. 343,

Zeitschr. f. Physik, vol. xiii, p. 351, 1923.
1923
H. A. Kramers and
112
S3=const.
(3)
The
kinetic energy is
T=H(dD)+coQ];
(4)
on substituting the expressions
T-|[AA
(5)
becomes
(1) this
+AA +AA
2
+Ao>(ad)+a>i}].
In order to obtain the energy as a function of the components of the

angular momentum we substitute in (5) the values of d*, d v d z cal,
culated from
(1)
We calculate w by deducing a relation between

O
plying the equations

this
and
(2)
(1)
by
~,
aj
and
(da)
by multi-
a*
-^, -^respectively, and adding;
from
'A,
we get
aJD,
Ax
_
A
A~
and obtain therefore
~~~
U, r +S
ni M^
"
A,
T
2
W-v^,^
k.,2
A
**-]/
A
-**-S
2
a
<*JR
1
J
x\.
-^-a*
C*|/
<*2
~^^y
~^z
Besides this integral, we have the principle of the conservation of

the angular momentum which gives
:
(7 )
=J) X
+D y +D,
2
-const.
The general character of the motion can be summarised as follows

The components of D are the co-ordinates (relative to the axes (#, y, z)
:
fixed in the top) of the point in which the invariable axis of the
system (i.e. the axis of resultant angular momentum, which is fixed in
This point traverses the curve of

space) penetrates the sphere (7).
intersection of the sphere with the ellipsoid (6), which is rigidly
connected to the top. In the fixed co-ordinate system, therefore,
x, y, z system of axes, fixed in the top, executes a periodic nutation superposed on a precession about the axis of resultant angular
momentum. In the case where the sphere touches the ellipsoid the
the
motion becomes a rotation about a permanent axis.

In order to formulate the quantum conditions for the motion we

must return
to the co-ordinates
ing momenta.
function of 0,
(2),
we suppose
If
</),
and
t/j
9,
113
$ and calculate the correspondT expressed as a
^,
the kinetic energy
their derivatives,
by means
of the relations
6,
d -=0 cos
>r
& y -=9 sin
(/)
t/j
A z =--(j)-[-ifj cos
we obtain
sin 6 sin
<
sin 9 cos
<
(f)~\~i(f
0,
_ar_aT
'~dd~~d& t
aT aT
<n
T
rn
ad.
aT d& v
aT ad 2
lrt
ttiylri
a<
aT d& y
aT
_ _ ad^
_
a<
ad,
a</r
ad x
____
ad y
a</>
ai - aT ad x
__
ai/r
__
..
ad,
__ _
7
ad 2
a</>
a<
__ _ _
aT ad
aT
ad,*
ad,
a^
ad y
dj>
aT
by (5), the derivatives of T with respect to d.r, d d, are the

components D x D^, D z of the angular momentum (1), it follows that
Since,
tf ,
cos
=rDa; sin
<
sin
<^
D y sin
cos
+-D~ cos
Since the constant angular momentum can have an arbitrary direction in space, the motion is degenerate and we can reduce the number
of degrees of freedom by I.
can, for example, without loss of
axis
choose
the
fixed
of the Kulerian co-ordinate
generality,
polar
We
00
in the direction of the resultant angular
system
which case we get
momentum
D, in
D^Dsin 0sin0
D v =-Dsin0cos</>
D,=D cos
(8)
(D= D
|
|),
and the momenta become
P^= cos
p.=Q.
Cos is determined as a single valued function of 0, owing to the
fact that a curve on the ellipsoid (6) is prescribed for the end point
8
114
and that
of D,
revolution of
<f).
curve will be traversed just once during one

It will be seen then that the motion is separable
this
in the co-ordinates 9, $,
$p
and
diff=-27rT)
to the
and leads to the action
conditions
l
:
D$ cos
(10)
integrals
cos
$jyfy=D$
quantum
<f>,
ed<f>=n*h
The second quantum condition admits of a simple interpretation.

The surface on the sphere (7), which the point of the vector D
passes round in a negative direction of rotation, is given by
F=-D JJsin ed0d<f>=D*tfd(cos 0)<fy.

a
If
integration with respect to 0, we obtain,

of the surface does not enclose the polar axis
we carry out the
boundary
if
the
FD
n*
2! cos 0dJ>=27rD
T
if it
encloses the positive polar axis
if it
encloses the negative polar axis
and
if it
m
:
m
encloses both ends of the polar axis
F=D $(2-cos 0)<ty=27rD 2 --,
In
all
cases the ratio to the hemisphere
is
where n is a whole number, and the second quantum condition can

be formulated as follows the ratio of the surface cut out from the
:
sphere
(7)
by
the vector
n can take the values
0, 1
to the hemisphere
is
equal to
n/m
... 2m.
1
In the case of the top we do not denote the quantum number of the resultant
angular momentum by j, as in the general theory, but by w, because this letter is
used to denote the terms of a molecular rotation spectrum (see Rotator, 12).
115
We shall now apply our considerations to the case
of an ordinary
For the components of the angu-
1
top without an enclosed fly-wheel.
lar
momentum we
the equation
obtain, in place of (1)
(5) for
the energy becomes
T=HAA +AA
2
On introducing the components
of angular
momentum,
,_a-w
+ A + vi
A
K }
21 x
y
If in this case also
resultant angular
we take the fixed polar axis in the direction of the

momentum, the relations (8) are again valid and
we have
T=
(13,
We get two
(U
v
quantum
conditions
\
'
Dj> cos
In the second condition we have to write cos 9 as a function of <f>

with the help of the energy W, which is equal to T since there are no
external forces.
It follows
from
(13) that
OA\7
^_
C080 =
'
2 JL
Lj
A*
AV
COS 2
(/)
'
A,
A,
A,
and the second quantum condition becomes
(15)
It leads to
The
meter.
an
containing the energy W as paraW as a function of the quantum numbers
elliptic integral,
calculation of
m and n cannot be carried out explicitly, except in the case of rotational

1
symmetry (A^
Av
which we have already dealt with
6).
See F. Reiche, Physikal. Zeitechr., vol. xix, p. 394, 1918; P. S. Epstein, Verh.
phys. Ge*\, vol. xviii, p. 398, 1916 ; Physikal. Zeitechr., vol. xx, p. 289,
d. Dtsch.
1919.
116
In this case,
tj>
will likewise
quantum
AÂ^,
the energy (13) becomes
be a cyclic variable and 6
conditions are
is
constant.
From
(14),
the
mh
27T
Dcos0=
nh
;
therefore
cos#=
we have
a kind of space quantisation, for which the angular

precesses not about an axis fixed in space but, relative
to axes fixed in the top, about the axis of figure. As a function of
i.e.
momentum
the quantum numbers the energy becomes
If one considers how the co-ordinates of a point of the top are exand (f> (by finite Fourier
pressed in terms of the cyclic co-ordinates
series), it will be seen that, in the series for the electric moment,
and v^ occur in general with the coefficients and

v^
The quantum numbers n and m can therefore change by and
When the electric moment has no component parallel to the
the frequencies
1.
1.
is excluded.
axis of figure the transition Aw
An application of the energy equation (16) to multiply atomic
molecules would give several systems of rotation bands, displaced
from one another by fixed amounts, with the arrangement of
lines in
type
At
any one band
(c/.
satisfying a formula of the simple Deslandres
12).
this stage
we
raise the question
how
it is
possible to derive
from the top formula (16), by a limiting process, the formula (1), 12,
for the rotator, and we shall show to what extent the application of
the rotator formula to a diatomic molecule is justified. If we have
the ideal case of a system consisting of two rigidly connected particles, then we have to put A a =0 in the top formula (16), and, in
order that the energy
may remain finite, n can take the value
We obtain then for the energy the previous rotator formula (1),
only.
12
117
Actually, however, in the case of diatomic molecules, we have to

deal with systems where, in addition to the nuclei which are practically points of large mass, a
number
which
of electrons are present,
move around
the nuclei and may, under certain circumstances,

possess angular momentum about the line joining the nuclei. This
system may be roughly compared to a top, whose moment of inertia
about the nuclear axis is small in comparison with the moment of

A^ about a perpendicular direction. For an invariable electron
inertia
configuration, the quantum number n, and consequently the second

term in the energy (16), is a constant. For the dependence of the
energy on the state of rotation we have therefore
W=W
(17)
A2
e
In general, in a quantum transition n, and consequently the contrithe motion of the electrons, varies, and
bution
e to the energy from
If we leave undetermined the
1.
varies
or
this
m
from
by
apart
of W, on the quantum numbers, since the conception of

the electrons as a rigid top is naturally very doubtful, we obtain for
the frequency radiated in a transition (neglecting the frequency v=ve
dependence
corresponding to
Am
0)
and so ve is very large in comparison with the term originatfrom

the rotation, on account of the smallness of A z in (16).
ing
Since the rotation term alone gives rise, as already shown, to lines
hi the infra-red, the spectrum represented by (18) is displaced towards
higher frequencies, and so may lie in the visible or ultra-violet regions.
We have in this the simplest band formula which represents to the
r
roughest approximation the observed bands.

separation of the lines the moment of inertia
may be
From
A,,,
the observed
of the molecule
calculated.
In passing from the energy equation (17) to the frequency equation

(18), the assumption is made that the moment of inertia A^ does not
vary with a change in the electron configuration. If this assumption

be dropped and we assume that A,,, changes from Aa W to AB 8 ), we
(
get, for
Am=l,
the frequencies
118
V=Ve
(19)
where
=?+
h
b=-
(20)
87r*\A,0)
X W/'
"
"
The frequencies (19) constitute the positive and negative branches
"
"
null branch
is obtained
of the band. For Aw=0, the
:
It
is
absent
if
the electric
moment
of the molecule is perpendicular
to the axis of rotation.
We
obtain the distribution of the lines in the three branches by

and
signs) and (21), and
drawing the three parabolas (J9) (with
1
on
the
i>-axis from the points
dropping perpendiculars
corresponding
to positive integral values of
m (see fig.
8).
One
of the
two branches
the lines are concentrated (with

(19) covers part of the v-scale twice,
"
band-head." The line in
finite density) at the reversal point, the
which the positive and negative branch intersect (m 0) is called the

"
null line." To calculate the moment of inertia from an observed
band, the constant b must be known, and for this one must know the
If a null branch is present its
position of the null line of the band.
null line.
position serves to indicate the
If,
however, the null branch
absent, the properties of the band given here do not suffice. It

appears, however, that the intensities on the two sides of the null line
is
are symmetrically distributed, and the null line itself has the intenwe shall return to this point again shortly.
sity
Kramers and Pauli have endeavoured to treat the band spectra of
molecules whose electronic angular momentum has a direction fixed
;
in the molecule
but
absence of the null
is
line,
otherwise unrestricted, and to explain the

by applying to molecules the model of the
top with an enclosed fly-wheel.

The top represents here the nuclear system (considered rigid) and
the fly-wheel represents the angular momentum of the electrons.
Since the dimensions of the electron orbits in a molecule are of the
1
Comp. A. Sommerfeld, Atomic
Structure
and Spectral Lines (Methuen),
p. 427.
PERIODIC
same order
AND MULTIPLY PERIODIC MOTIONS
magnitude as the nuclear separations, and the mass of

small in comparison with that of the nucleus, A is a
small
in comparison with A^, A v A z
the quantum
magnitude
of
the electron
is
conditions require, moreover, that the angular
momentum
13 of
the
rn
O12 3
6
Band
FIG.
electrons shall be of the
8.
same order
of
magnitude as the resultant
angular momentum D.
We now develop T in powers of A and break ofE the series after the
second term
The first term of this expression

electron motion), the second term
is
a constant (the energy of the
120
E=
(22)
the energy of the gyroscopic motion of the molecule.

The stationary motions are obtained when mlift-n is put for the
resultant angular momentum |D| and the values of E so chosen that
is
the ellipsoid represented by (22), whose centre is at the point 12a, cuts
from the sphere |D|=const. a surface whose ratio to that of the
hemisphere
is
n/m
we
shall return later to the consideration of the
and the question

significance of
jected to a quantum condition.
whether this quantity
is
to be sub-
In the case of diatomic molecules we take the z-axis in the line

and the #-axis in the plane determined by the
joining the nuclei,

axis of the angular
Ay
momentum
of the electrons
We then have a w =0, A
and the
line joining
small in comparison with A^ and

(in the ratio of electron mass to nuclear mass), and (to the same
the nuclei.
approximation) Aa.=A y
The
ellipsoid represented
by
(22) degener-
ates into a flat circular disc, parallel to the (x, y)-plane, having
0, 2a 2 as the co-ordinates of its central point.
Ua x
The curve of intersection of this degenerate ellipsoid with the

sphere encloses a surface the ratio of whose extension in the z direction to the radius of the sphere
ant angular
number
is
VA
momentum D which are
n=0
is
permissible.
For values of the resultZ /A X

not too great, only the quantum
.
This signifies that the
flat ellipsoid
touches the sphere. If E be allowed to increase from to oo such a

contact occurs twice, irrespective of whether the centre point of the
,
ellipsoid lies inside or outside the sphere. Of the two corresponding

types of motion only that corresponding to the smaller value of
stable, since only in this case will the curve cut out from the sphere
for a small increase of
be closely confined to the region surround-
is
ing the point of contact, i.e. the motion remains in the immediate
proximity of the stationary motion.
The point of contact must lie in the plane passing through the
middle point of the ellipsoid and the nuclear axis

that D v =0. We conclude from the relation
from this it follows
which implies that the normal to the sphere coincides with that of
the ellipsoid at the point of contact, that
Da-a^

is
of the order of
magnitude
It will be seen
from
fig.
We
A^/Aa..
third term in the energy formula (22)
121
can therefore neglect the
and write
9 that for this
we can
write also
E=
If the
quantum number
be
introduced together with the

quantities
and
defined
by
Oa,
-,
ZTT
Dx
it
ollows that
FIG. 9.
(23)
This
is
rotator,
a generalisation of the formula for the energy of a simple

which is obtained by putting
==0.
If the angular momentum of the electrons
nuclear axis (0), then
is
directed along the
This formula agrees with that for the symmetrical top
term there proportional to

put equal to
(as electron energy)
(16), if
the
be removed and
n.
The general formula (23) has been used in different ways by

1
and Kramers and Pauli, 2 to explain the observed
Kratzer,
phenomena, that, in a system of equidistant band lines, one line
is
missing.
Kratzer uses the formula (23) for the case where =0, i.e. the angular momentum of the electrons is perpendicular to the nuclear axis.
From
1
2
A. Kratzer, Sitz.-Ber. Bayr. Akad. Math.-phys. KL, p. 107,

H. A. Kramers and W. Pauli, jr., Zeitschr.f. PhyM, vol. xiii,
3, 1922.
p. 351, 1923.
122
he obtains for the frequency radiated in the transition

(keeping the electron configuration constant)
^+_*_(m _
(24)
and
+t
),
for the frequency radiated in the transition
(25)
= ?.__.(m
The positive and negative branches

lines,
which begin in general at
consist therefore of equidistant
different places
the positive branch
().
the negative at
By forbidding the state
and putting ~\ Kratzer thus deduces a gap, of twice the
begins at \
w=0
m->m+l
width of the ordinary separation of the
lines,
between the two
branches.
Kramers and Pauli show that

does not vanish.
In
this case
this
remains essentially valid
must be
> and
if
the expansion of
E in terms of 1/m,
remains approximately valid even for small values of
m (except for
2
m=0, which
cannot occur
if
=)=
0)-
If
we
neglect the term
we
obtain the same frequencies (24) and (25) as above, thus also the
correct size of the gap in the case f =J.
The value =% can arise by the angular momentum of the electrons
being h/fa and making an angle of 30 with the nuclear axis. This
assumption leads, however, to difficulties in connection with the
1
For this reason
intensities given by the correspondence principle.
Kramers and Pauli return to the assumption =, =0, in other

"
"
words to an electron momentum (with a half quantum number)
perpendicular to the nuclear axis.
20.
Coupling of Rotation and Oscillation in the

Case of Diatomic Molecules
The bonds between the atoms which are combined to form a molecule have hitherto been regarded as rigid this is only approximately
;
There are other difficulties, inasmuch as an electron angular momentum which

not parallel to the nuclear axis is only possible for certain degenerations of the
electron motion (M. Born and W. Heisenberg, Ann. d. Physik, vol. Ixxiv, p. 1, 1924).
Prof. W. Pauli informs us that the rigorous treatment of these degenerations leads
to parallel and perpendicular orientations only for the angular momentum of the
1
is
electrons.

true, however, for the
atoms
will in
123
fact execute small oscilla-
tions with respect to one another. The problem now is to find what
influence these oscillations have on the energy and on the frequency
of the radiated or absorbed light.
The actual nature
of the forces which bind the molecule together

be determined in an extremely complicated manner by their
electronic and nuclear structure. Here we shall make the simplest
possible assumption, viz. that the atoms may be regarded as centres
of force which act on one another with a force depending only on the
it can be shown that the results so obtained represent a
distance
will
correct approximation to the actual behaviour. 1

As regards the angular momentum of the electrons in diatomic
molecules, we have seen in the previous paragraph that it has no

influence on the rotational motion of the nuclei, and gives rise only
to an additive term in the energy if its axis is parallel to the line
joining the nuclei. The same
oscillations in this direction
must be true when the
we
nuclei perform
shall therefore restrict ourselves
here to this case.
We
consider, therefore, a diatomic molecule, consisting of
two
massive particles mi and 2 separated by a distance r, between which

there exists a potential energy U(r).
It
may
may
be shown quite generally, that such a two-body problem

We choose the centre of
be reduced to a one-body problem.
and detergravity of the two particles as the origin of co-ordinates

mine the direction of the line joining
l by the polar co2 and
then
and
r z are the distances of the particles

from 0, their polar co-ordinates will be r l9 0, <f> and r 2 , TT 0,
and further, r 1
The Hamiltonian function becomes
2 =r.
ordinates
0,
(f>.
If
+r
sin 2
9)+('
^+r+r^ sin
A
t
0)
+ U(r)
sin 2 0)+U(r).
Since r x and r a are measured from the centre of gravity,
and therefore
be substituted in H, we get
If this
1
M. Born and W. Heisenberg, Ann.
d.
1,
1924.
124
H=
(1)
(*
2
+r*fc +r*<f>* sin
6)
+ U(r),
on writing
Now
the expression
the Hamilton ian function of the motion

under the action of a centre of force from
(1) is
mass
of a particle of
/x
which it is separated by the distance r.

In the following chapter we shall investigate
we
here
shall consider only the case
this problem quite

where a position of
generally
stable equilibrium exists, this being the only case of importance in
connection with molecules. 1 There will then be a distance r for
;
which U(r)
is
minimum,
i.e.
(3)
quantity at r
A possible
'=0,
">0,
denotes here, and in what follows, the value of a
where the index

r
motion of the system is a rotation with a constant nuclear separation r and a uniform angular velocity
about
of the masses
a fixed axis, passing through the centre of gravity
and perpendicular to the line joining them (nuclear axis). We take
the axis of rotation as the line 0=0, and have
state of
<
(4)
where the bar denotes here, and in the following, the value of a quality
We
take this motion as the starting-point for an approximate

of dealing with small oscillations. We suppose the separaincreased by a small amount x so that r=r -\-x, and develop the
method
tion
/"
and the correHamiltonian function, regarded as a function of x,

of
x.
The
Hamiltonian
function is
in
momenta,
powers
sponding
(f>
The momentum
associated with
angular
(/>
is
momentum
constant, because <f> is cyclic

for x=Q, therefore
moreover,
is
the
P=/"Vo-
(5)
The momentum corresponding to x

1
M. Born and E. Huckel, Phyaikal.
Kratzer, Zeitschr.
/.
Physik, vol.
iii,
is
Zeitechr., vol. xxiv, p. 1,
pp. 289
and 460,
1920.
1923
see also A.
125
p x =t*x.
Consequently
On expanding
The
in
coefficient of
powers of x we get
x vanishes since by
^,2
(7 >
(4)
and
(5)
^=u';
the Hamiltonian function has therefore the following form
H=W +^+|
(8)
where
(9)
This reduces the problem to that of the non-harmonic oscillator,

which we have discussed in 12.
If
we now
introduce angle and action variables
we have
to put
w x and 3 X in place of x and p x in the manner

explained for the non-harmonic oscillator. If we take into consideration the terms in x* in (8), we find (cf. (9),
12)
and then to introduce
H =W
(10)
J)
+ JX J) + J>( J),
where for shortness we write
we take into account the term 6x4 H assumes to the same

approximation the same form, only a dependsâlso on b. The functions
(J) and v(3) are found by calculating r as a function of p
Similarly,
if
126
or J from (7) and substituting in (9). Actually in order to calculate

them the function U(r) must be known exactly. If we restrict ourselves,
however, to such small velocities of rotation that the deviation

caused by the centrifugal force, is small in comparison
=r 1
TQ, our objective may be attained by means of an expansion in

terms of r r Since
'=0, equation (7) may be written, to a first
with
approximation
from
this
we obtain
J2
47rV
Further
therefore
also
can be expanded in the form
We have
omitted here
The energy
all
terms of order higher than the
as a function of the action variables
first
in
J2
now becomes
where A=/u,r 2 is the moment of inertia in the rotationless state, and

v and a have the meaning assigned above.
2
If we neglect the terms in J x 2 and J^J and consequently the nonharmonic character and the dependence of the v's on J, the energy is
resolved into a rotational component and an oscillation component
,
of the
well-known form.
pendence
of the
number and
As a nearer approximation we have a defrequency on the rotation quantum
oscillation
also the
non-harmonic character of the
oscillation.
Naturally our method admits of more accurate calculations of the

energy, involving higher powers of
J and J c
We
127
shall apply the results obtained to the spectrum of diatomic

In the stationary states they have the energy
molecules.
W=U
(12)
m is the rotation and n the oscillation quantum number.

The frequency corresponding to the transition
where
For fixed values of the initial and final oscillation quantum numbers
n 1 and n 2 and varying values of the rotational quantum number m,
this gives a band with the branches (to which a null branch may be
added)
v=abm+cm
(14)
where
a, 6,
(20),
19.
and
have a somewhat
2
,
different
meaning from that in
The frequencies
(15)
V^VQ^
n 2 )+ha Q (ni*
n 2 2 ),
which can be ascribed to the change of oscillation quantum number

alone and so may be called " oscilktion frequencies," are displaced
from the null line of this band by
Thus we obtain a band system which
is
made up
of individual
bands
and n 2 The positions of

corresponding to the series of values of
the individual bands in the system are given by (15), while (14) gives
.
the law of arrangement of the lines in the individual bands.

The infra-red spectra of the halogen hydrides are of the type described here but without null branches. 1 These spectra consist of
"
individual
double bands," i.e. an approximately equidistant succession of lines, which are symmetrically situated with respect to a gap.
In this gap we have to imagine the null line mentioned in

19.
doubling-back of the one branch is not observed in this case.
1
Measurements, especially by E. S. Imes, Astropkys. Journ., vol. 1,

For the theory of A. Kratzer given hore, sec Zeitschr.f. Physik, vol. iii,
See also H. BeU, Phil. Mag., vol. xlvii, p. 549, 1924.
p. 251, 1919.
p. 289, 1920.
128
The
oscillation frequencies in the case of
"
v=:5657
(in
wave numbers,"
i.e.
number
HC1
of
are at
v=2877 and
The
waves per cm.).
corresponding bands appear in the case of absorption at the ordinary

temperature. They correspond, therefore, to a change in the oscillation
quantum number
that
it is
ture
for
which the
initial state
has so
little
energy
present to a considerable degree at the ordinary tempera2

that, however, can only he the oscillation state n --0.
We
assign, therefore, to the
two bands observed the two transitions
for absorption, or the values

for emission.
and n 1 =2
respectively,
and n 2 =0
In accordance with the theoretical formula (15)
the second band
is
not situated exactly at twice the frequency of the
first.
An alteration of the rotation and oscillation quantum numbers

may be accompanied by a simultaneous alteration in the electron
configuration of the molecule.
A frequency
corresponds to a transition between two stationary states with the

energies
where
vl(tt ---
(18)
Altogether we obtain a band system whose individual bands exhibit

the structure described in
19, and are arranged according to the
formula
(17).
Written somewhat differently,
it is
Since, in general, i> 01 and v 02 are of the same order of magnitude and
their difference is small compared with the values themselves, the
first
"
"
the most important. It defines the position of a

band
in the band system
a group contains, therefore, all bands
term
is
group
for which n changes by the same amount.
;
The next term
defines
the individual bands, inside the band group, in terms of their final
quantum numbers,
129
A beautiful example of a band system is provided by the violet

1
cyanogen bands. Fig. 10 gives the positions of the null lines and
Offit
123VS
OiZ
FIG. 10.
their wave-lengths
number
1
the
first
row underneath the oscillation quantum

row that in the final state. 2
Explained theoretically by A. Kratzer, Physikal.

d. Physik, vol. Ixvii, p/127, 1922.
According to A. Kratzer, loc. cit.
Ann.
2
in the initial state, the second
Zeitechr., vol. xxii, p. 552,
1921
THIRD CHAPTEK
21.
Motion in a Central Field of Force
THE applications of the principles of quantum mechanics, developed

in the second chapter, are at present considerably restricted, owing
to the fact that these principles are concerned only with multiply
periodic systems. The first example dealt with by Bohr, namely,
systems consisting of a nucleus and a single electron (the hydrogen

satisfies this condition of
atom and the similar ions He + Li ++
,
periodicity.
etc.),
In the case of other atoms the same
difficulties
underlie
an examination
body problem
of the periodic properties as in the case of the manyof astronomy, and we can proceed only by a method
number of atomic
which exhibit themselves in the series
be explained on the hypothesis that one electron, the
of approximation.
Bohr
realised that a large
properties, especially those
spectra,
"
may
"
"
or
series electron/' plays a special role in
radiating electron
the stationary states under consideration. The essential feature of
is that this one electron is in an orbit, which, at any
"
x
rate in part, is far removed from the rest of the atom, or
core,"
shall always
and exerts only a small reaction on the latter.
these states
We
speak, therefore, of the stationary orbits of the radiating electron,

since we neglect the changes taking place in the core. The spectrum
of the atom corresponds then to transitions of the radiating electron
from one orbit to another.

This assumption implies that the motion of the outer electron is
multiply periodic, and that, in traversing the core, the electron
neither gives up energy to nor receives energy from it. Motions of
this kind are quite special cases according to classical mechanics, for
the motions of the core electrons must be such that their energy is
the same after every period of the outer electron, a condition which
1
German, Rumpf. The English equivalent of this word is not completely
standardised: the alternatives "body," "trunk," "kernel" have been used by
different writers.
130

is
evidently fulfilled only
131
strictly periodic solutions of the comSince, however, a large number of obser-
by
plex many-body problem.

vations may be explained in a surprisingly simple way by such
stationary orbits of the radiating electron, it appears that we are
here dealing with some general process, which cannot easily be explained
by such
We
have here the same

singular types of motion.
mechanics as was brought to light by Franck's
failure of the classical
the exchange of energy between

researches on electron impact
electron and atom, or atom core, is restricted in a manner similar
;
to that familiar to us in the energy interchange between an
atom
and radiation.
At present we cannot express
this non-mechanical behaviour in

endeavour to substitute for the atom a model which
possesses, in common with the actual atom, this characteristic property of the absence of energy exchange between core and electron,
and to which the principles of the quantum theory, developed in the
formulae.
We
second chapter, are applicable. The simplest assumption is that the

action of the core on the radiating electron can be represented by
a spherically symmetrical
field of force.
Further development has
shown that this simple hypothesis suffices to provide an explanation

of the main characteristics of the spectra of the first three divisions
of the periodic table and their sub-groups. The conception of a
"
is, however, no longer adequate to
radiating electron
of
the
the
elements, but these consideraremaining
explain
spectra
tions are beyond the scope of this book. 1
"
single
For
this reason
we
shall
now
deal with the motion of a particle in
a central field of force. The motion in a Coulomb field of force (such

as we have in the case of the hydrogen atom) will be found from this
as a special case.
So far as the calculation
is
concerned
it is
immaterial whether
we
consider our problem as a one-body or as a two-body problem. In

the first case we have a fixed centre of force, and the potential of the
field of force is a function U(r) of the distance from the centre. In the
second case we have two masses, whose mutual potential energy U(r)
depends only on their distance apart they move about the common
;
centre of gravity. As we have shown generally in

20, the Hamiltonian function in polar co-ordinates is precisely the same for the
two cases, if, in the one-body problem, the mass p of the moving
1
For the development of the theory of complex spectra, see H. N. Russel and
F. A. Saunders, Astroph. Journ. t vol. Ixi, p. 38, 1925 ; W. Pauli, jr., Zeitsch. f.
Phys., vol. xxxi, p. 765, 1925 ; W. Heisenberg, Zeitschr. f. Phys., vol. xxxii, p. 841,
1925; F. Hund, Zeitsch. f. Phys., vol. xxxiii, p. 346; vol. xxxiv, p. 296, 1925.
132
body and its distance r from the centre are used, and
body problem /* is defined by the equation (2), 20,
if
in the two-
-=-+-,
m m
'
/LC
between the two masses. The following equaadmit then of both interpretations.
We work with polar co-ordinates r, 6, and <f>. Making use of the
canonical transformation (13), 7, which transforms rectangular into
and
r is the distance
tions
polar co-ordinates,
we obtain
for the kinetic energy,
22*5
where p r pe p^ are the momenta conjugate with
,
We arrive,
of course, at the
r, 0,
same expression when we
respectively.
calculate from
sn 2
2
the
momenta
and use them
to replace
r, 9,
<f>.
The structure
of the
Hamiltonian
function
shows that
r, 0,
<f>
are separation variables.
If
one puts
S=S r (r)+Se (0)+S/<),
(2)
the Hamilton- Jacobi differential equation
splits
up
into three ordinary differential equations
which can be solved for the derivatives of S
133
d$ r
W denotes the energy

==xr sn
Of the three integration constants
is
the angular
momentum about the polar axis (i.e. the line 6=0), and
the magnitude of the resultant angular momentum. Since also

the direction of the angular momentum is constant (as in
every
system subject to internal forces only), the orbit is plane and the
is
normal to the plane

the angular
(r,
<)-plane
of the orbit is parallel to the vector

representing
inclination i of the orbital plane to the
momentum. The
is
given therefore by
a>4=a,
cosi.
We consider next the general character of the motion and then

determine the energy as a function of the action variables for the
case of a periodic motion and, finally, we consider the
progress of the
motion in time.
The co-ordinate is cyclic and performs a rotational motion

(cf.
The co-ordinate 6 performs a libration or limitation motion in
an interval, symmetrical about w/2, whose limits are given by the
(f>
9).
zero points of the radicand in the expression of

sin
0=-_*
a
= cos
i,
pe
i.e.
by
0=--j-i.
2
Further, the character of the motion depends essentially on the behaviour of the radicand in the expression for p r
,
We
investigate the various possible cases on the supposition that

U(r) is a monotonic function of r and that the zero of potential
energy is so chosen that it vanishes for r oo .
134
Case 1. In a repulsive central field of force U(r) is positive. In

must be posiorder that positive values of F(r) shall occur at all,
tive. F(r) will then be positive for large values of r, decreasing confor small values of r, F(r)
tinually with continuously decreasing r
F(r) has therefore exactly one root. The

certainly negative
motion takes place therefore between r=oo and a minimum value
is
of
r.
Case 2. In an attractive central field, U(r) is negative, and

may be positive or negative. The sign F(r) for large values of r
W
is
determined by W. For positive W, F(r) is positive there, and there

are motions which extend to infinity. There are no such orbits for a
the variation of U with r, and, in
negative W. In the case of
W=0
certain cases, the magnitude of a e is the deciding factor. The sign

of F(r) for small values of r depends on the rate at which U(r) becomes infinite. If, for small r, it increases more rapidly than 1/r2 , 1
,
F(r) will be positive there, and there will be orbits which approach
if
indefinitely close to the centre of force
U(r) becomes infinite
more slowly than J /r 2 there will be no such orbits if U(r) ap;
2
proaches infinity as 1/r the magnitude of a e is the deciding factor.
there
are
cases
Further,
where, in addition to paths extending to the
centre and to infinity, orbits exist which extend between two finite
,
and non-zero values of r, rmm and r max this is the case when rmin
and rraax are consecutive zero points of F(r), between which F is
positive. In the case where U(r) becomes infinite more slowly than
2
for which such a libra1/r it is certain that there are values of
for negative
tion sets in
there are in fact, in this case, no other
;
motions but
librations.
many applications to atomic physics we are only concerned

with those motions in which the electron remains at a finite distance
from the centre and which are periodic. We consider therefore in the
In
W values such that
following only the case of attraction and take for

F(r) is positive between two consecutive roots rmm
and rmax
In this case we can apply the methods developed for periodic

motions.
We
obtain the action integrals
1
the order of
Mathematically expressed, this has the following significance
2
magnitude of U(r) is larger than that of 1/r for small values of r. The order
of magnitude of a function f(x) (>0) is greater than the order of magnitude of the
:
function g(x) (>0), for small values of x,
/(*)
and
g(x)
if
have the same order of magnitude
if
the limiting value of
-j-r-
r is
J\^f
finite
constant.
(4)
136
=
J
J/)
With the help
of the substitution
a
1
i
ae
the second integral takes the form
Jn=
The evaluation
of this integral
and
(cf. (3)
J^M**
We
(8),
Appendix
II) gives
%)
can now express a e and a in terms of the action variables
In order to find the energy as a function of the J's we should have

to solve the equation
(6)
for
is
W.
This
is
it
impossible without a detailed knowledge of U(r)
on
and
J
the
combination
r
depends only
;
seen, however, that
J0+J
The two frequencies
aw
are therefore equal and the system is degenerate. In accordance with
the fundamental principles developed in
15, we introduce new
variables
l9
w 2 w& and J 1? J 2 J 3
,
so that w.3
is
constant.
We
arrange at the same time that, in the case of the Coulomb field of
force, where vr =v &
v^ that the variable w 2 shall also be constant.
We write,
therefore, in accordance with (8),
136
W l =W r
W 2 =W e -Wr
(7)
Jl=Jr+J0+J
J 2 =J0+J,
J3 =J,-
W3=w*We
The equation
(6)
contains then only
energy W in the form
J x and J 2 and we derive the

,
W=W(J,, J 2
(8)
).
For the stationary motions we have, provided there is no further

degeneration (e.g. no Coulomb field), the two quantum conditions
:
is
called the principal
quantum number and k the
subsidiary quan-
tum number. 1
The action variables have the following physical significance J 2
times the total angular momentum, J 3 is l/2ir times its com:
is 1/27T
ponent in the direction of the polar axis.

It is obvious that J a cannot be zero. Also J 2 =0 would signify a
"
motion on a straight line through the centre of force, a pendulum
"
in physical applications, where the centre of force

motion
atomic nucleus, this case must of course be excluded.
;
is
the
In order to find the physical significance of the angle variables,

calculate them with the help of the transformation equations
we
as
If
we introduce the
J^'s in the equation (3)
we obtain
47rV 2
T 2
JrO
'
sin 2 6
and
for the angle variables
putting v l
=-
1
k is also called the azimuthal quantum number.
fact that it can also be put in the form
where
is
This term arises from the
the azimuth of the moving point in the orbital plane.

r
137
*- c
-7
r
1
(10)
"J
J- a sin 2
The two
integrals in dO
may
dO
= sin"
T 2
Jo
cos 6
;_~
'
We have
be evaluated.
(10/)
fl
r+const.
sm^
sin 2
(9
and
=
(10")
sin 2 6
V'-.J
sin
dO
2
2
/*
Jsin
J
= sin*
It will
cos
(cot
cos 2 !
""sin
sin 2
i
cot 0) +const.
be seen from fig. 11 that, apart from the arbitrary constant
of integration, the integral (10') is
the angular distance if/ of the moving

point from the line of nodes,
measured on the orbital plane, and
the integral (10")

of this angular
(r,
<)-plane.
By
the projection
separation on the
is
subtraction of this
we get the longiprojection from

tude of the line of nodes. The third
<f>
of our equations (10) states, there-
apart from an arbitrary

additive constant, the longitude of the node
FIG. 11.
fore, that,
the second of the equations
(10), 2irw z
is
is 27rt0 3 .
According to
the angular distance
of
138
the moving point from the node, measured on the orbital plane, inby a function of r
creased
J 1? J 2 )
For given Jj and J 2 F 2 is a single- valued function of r, for, during

a libration of r, Jp r rfr increases by Jj
the partial derivative with
,
respect to J 2 assumes, therefore, its old value once more. Apart from
an additive constant, 27rw 2 is consequently the angular distance of a
point of the path with a given r from the line of nodes, measured on
the orbital plane, and therefore, apart from a constant, the angular
distance of the perihelion (r mm ) from the line of nodes. Finally, again
apart from an additive constant, 277^ is what astronomers call the
"
mean anomaly," namely, the angular distance from perihelion of a
point imagined to rotate uniformly and to pass through perihelion

simultaneously with the actual moving point.
Since we have a system subjected only to internal forces, and the
motion takes place in a plane, the angle variable w 2 associated with
,
the total angular momentum, occurs in the Fourier representation of

the electric moment with the factor
1 only (as was shown generin
We
can
see
this
also
17).
ally
directly, from the nature of the
These are
expressions for the angle variables.
J2)
^1=
fi(r, Ji,
w2 -
<A+/2 (r, J lf J 2 )
w3 =const.,
or, if
we
solve for
r,
i/r,
r=
lfj
= 2TTW
^(w
2
+(l> 2
l9
Ji,
J 2)
(W v J 1? J 2 ).
is
If we transform to the rectangular co-ordinates
where
r],
perpendicular to the orbital plane, we find for the components of the
electric moment p expressions of the form
,
(11')
P^=.
number k,
can
numbers
n
introduced
and
alter by
k
by (9),
quantum
while
n
in
amounts.
can
only,
general change by arbitrary
The orbit is best expressed in terms of the co-ordinates r and
According, then, to the correspondence principle, the
the
From
the
first
equation (10)
we
get
of
1
*//.

dw
139
UL
-,dr.
Also since the angular
we
momentum is J z /27r
eliminate dt and derive the differential equation of the orbit
27T
(12)
dr~
477
Since the motion consists of a

r, combined with a
uniform rotation of the perihelion,
the form of the orbit is that of a
libration of
rosette
(cf. fig. 12).
FIG. 12.
The Kepler Motion
22.
The simplest application
of the results of
21
is
to
atoms
consist-
ing of a nucleus with a charge Ze and only one electron. In this case
the motion concerned is that of two bodies under the influence of a
mutual attraction giving
V(r)
(1)
This motion
rise to
we
The action
shall
the potential energy
= ~-
now consider.
integral
Jr
(6),
21, takes the
(2)
where
A=2/*(-W)
(2')
27T
\2w.
form
140
It will be seen that only when

is negative can the radicand have
two roots between r=0 and r=oo enclosing a region within which it
is positive ;
consequently A, B, and C are all positive numbers. By
the method of complex integration we obtain (cf. (5), Appendix II) :
2n
ATT-
______
V-2W
We
can now express the energy
the value
we
find being
J
J
*
J'
J
..
fl
W in terms of the action variables,
w-
a\
The motion is therefore doubly degenerate, since for a given value

of J the energy is independent of J 2 (the total angular momentum)
Not only the longitude of the node, but also the
as well as of
J^.
angular distance of the perihelion from the line of nodes, remains
unaltered.
We
and expressed
have only one quantum condition,
in terms of this the energy
(4)'
v
is
-.
h*
The motion has only one frequency

we find for this
n*
different
from zero
from
(3)
_aW_477V i
the period of revolution
is
therefore
1
We again express the

orbital plane.
As
orbit in terms of the co-ordinates
differential
equation of the path,
we
r,
get,
ifj
by
21:
VC
d$
dr~
B
r\V/-A+2 r
I
where A, B, and C have the meanings
(2').
in the
C'
f
r2
Integration gives
(12),

.
and,
if
we
solve for r
_
If,
for shortness,
we
C-Br
141
write
we obtain
the well-known form for the equation of an ellipse, whoso

with the origin of the co-ordinates
focal point coincides
the eccentricity and I the semi-latus rectum or parameter.

express these in terms of the angle variables we have
is
If
we
--!-
(8)
These two quantities fix the form of the orbital ellipse. Since an
ellipse is usually determined by the semi-major axis a and the eccentricity e or by means of the two semi-axes a and 6, let us express a
and b in terms of the action variables. We have
T'2
(10)
1-e
47T*
6=aVl^
(11)
Of these two quantities a alone is fixed by the quantum condition

and with it I and 6, can assume all values consistent with the correand v lf
sponding a. The relation between a and the quantities
e,
likewise fixed
(12)
by the
quantum condition, can be expressed as follows
-,
142
The equation (13) expresses Kepler's third law. For the case of the
circular orbit, equation (12) states that the orbital energy is equal to
half the potential energy. As we shall see in a moment, it is in
general equal to half the time average of the potential energy.
We now consider the progress of the motion in time. By 10,
we
get for
wl
21,
w 1 =v l t+8 1 =
If
we
resolve the radicand into its linear factors,

r
we
obtain
prvidr
w 1 =\
jVA.V[a(l+)-r][r-a(l-e)]
for a(l
+e) and a(l
are the libration limits of
e)
(14)
r.
The substitution
cos u)
r =a(l
transforms the integral to
Wl
(15)
In order to make clear the geometrical significance of u, we introduce

such that the -axis is the major axis
77
rectangular co-ordinates
of the orbit and the origin is the centre of force, Z (fig. 13), thus
,
We obtain then from
(7)
= qr
-
(16)
fy
and
(14)
aq =a (cos u
a cos u
<" V
AA
wo
e)
WJ
=a Vl e sin u.
ON-a, ZQ-f =a [cos (ZON)-e]
2
77
In
fig.
13
QN=aVl
fl
sin (ZON).
and
QM=>q=Vl-
2
.
The angleZON is there-
fore just the auxiliary quantity u. On account of

u is called the eccentric anomaly.
its significance
Now that we have found expressions for all the

principal magnitudes of the Kepler motion we
shall write them down once more in collected
forjtn.
FIG. 13.
(3)
The energy
W=
of the
motion
is

the motion
is
143
confined to an ellipse with the semi-axes
T'2
=;
(10)
b=^
(11)
the parameter of this ellipse
is
Z=
(9)
the eccentricity
(8a)
and the
inclination
polar axis of the
The progress
r, 6,
of the
normal to the plane of the orbit to the

co-ordinate system is given by
of the
motion
is
given
(14)
r=a(l
(16)
ecosu)
a(cosu
iâVl-c
(17)
Here w
by
is
defined
e)
88 "^.
by
27Tv l
(150)
t=u
sin w,
where
being reckoned from the instant at which the perihelion is traversed.

A knowledge of the progress of the motion in time enables us to
calculate certain
mean values. Later we shall often require the mean

we now proceed to evaluate.
values of certain powers of 1/r which
We have
f- n
= l-= =
yn
l/yn-29
Now the areal velocity rîfi is equal to 2v x times the area of the ellipse,
from which
it
follows that
Vl dt
dj
and
if
n ==
144
For
n~2 we can
we take
1/r
quickly find, in this way, the mean value sought

from the ellipse-equation (7)
1
if
=1
Til
we
find
1
__
~ri
1
(19)
a 4 (l-e 2 )'
a 5 (l-e
The mean values r~ l
r, r
of the eccentric anomaly.
more easily calculated by means

Using (14) and (15)
.
are
rn
~fr vidta
If
cos u) n + l du
(1
2tTTj
and we
find
(20)
Mean
n^
values of the form r" cos m
by
anomaly
;
the ellipse equation

with the help of (18)
0(m>0)
(7'),
we
for
are best calculated for
n^m
by the
eccentric
obtain
/* cos m
and from
(14), (15),
r" cos w
and
0=ai
(16)
1 p
I
&7TJ
so that
(1
~
cos w) n m+1 (cos
c)
mdu

COS
145
r~ 2 cos iff=(
r-*cos0=-
(22)
Mean
values of the form r" cosw
For even values
of
J,
sin 2
i/j
sin'
vanish for odd values of
iff
may be replaced by
value reduced to the form just considered.
cos 2
/.
and the mean
In particular
/OO\
(23)
"
r-31 sln 92^,

I
We
can now find the time average
2o 3
of the potential energy, it is
and is thus twice the

becomes
This theorem that the
orbital energy.
mean
The mean
kinetic energy
is
kinetic energy
equal to half the
mean
valid generally for a system of electric charges

potential energy
which act on one another with forces obeying Coulomb's law.
is
Further, the co-ordinates of the electrical centre of gravity for a

charge revolving in a Kepler ellipse are the time averages of the
actual co-ordinates
and 77, thus
f=-30
(23')
and, by symmetry,
f,=0.
The
electrical centre of gravity is therefore situated
axis half-way between the middle point of the ellipse

not occupied by the centre of force.
on the major
and that focus
In the case of the Kepler motions the Fourier .series for the rectand for the distance r are comparatively
angular co-ordinates
rj
to
find.
that
r/a and g/a are even functions, and rj/a an
easy
Noting
uneven function of u, and therefore also of w l9 we can put
,
10
146
(24)
= JCo+Z C
*
cos
sn
For the
coefficients
we obtain
- cos
(27TW 1 r)dw 1
CT =4
- cos
(2rrw 1 r)dw 1
JQ
D =4
T
By
-J=
B T = -2
f*
--
D T -+
(16)
and
(17)
/V\
sin (27TW l r)d( -
7TTj
Now by
sin (27TW l r)dw 1
JoaVl e 2
we get from these
partial integration
ri r
B T =4
(25)
the integrals
>i
(*si
r*
^rJ
COS (Zrrwrfdl
r)'
__
I.
we have
\a
d(
=sin?/ du
= cos u du.
If
now we
introduce u as an integration variable from
obtain
7r
BT =
f
1
sin [r(u
sin u)] sin
u du
7TTJ
CT =
1
DT =
*
f
I
7TTJ
sin [r(u
sin w)] sin
rfw
cos [r(u
sin w)l cos
du,
"
2 f
I
7rrJ
A simple trigonometrical transformation leads to
(15),
we
B T = elf"
{I cos [(r+l)u
("
resin
u]du\
"
1 f
CT =
~f
1
DT =
TSinw|w+ J
cos[(r+l)w
cos[(r
re sin w"]dM+
cos [(r-\-l)u
cos
[(rl)uresinu]du\.
J
integrals appearing here are Bessel functions
J T (X) = 7T
cos (TH
rSinw]d!w}
1)?^
7TTlJ
The
resin u}du\
l)u
*
-
JQ
TTTl
cos [(r
147
defined
by
x sin u)du.
JQ
We have therefore
Since these formute
fail for.
r=0 we must
calculate
B C D
,
from
We find:
(25).
B -4
7"
f*r
7rJ
-^=a
(l-
2
-^ =-
f*l
C =4l
Ja
D
If, finally,
(24)
we
7r
=0.
we
derive
substitute the calculated values of the coefficients in

:
=l +
^+2 îW-JI^Tc)]
COS
(27^)
(26)
sn
28.
Spectra of the Hydrogen Type
calculations given in 22 provide us now with a basis for the

explanation of certain line spectra. According to the conception of
The
1
The Bessel functions are here indicated by Gothic J's t to avoid confusion with
the action variables.
148
atomic structure described in the Introduction, the hydrogen atom

in the uncharged (neutral) state consists of a nucleus of charge +e
e and small
and an electron of charge
and considerable mass
mass m. Of similar structure are the singly ionised helium atom

+
(He+) and the doubly ionised lithium atom (Li+ ), only the nuclear
charge is 2e and 3e respectively in the two cases. In all of these
atoms, therefore, we have a Z-fold charged nucleus and one electron
;
mechanics
consequently included in the theory given in

The energy in the stationary states is, by (4), 22,
their
is
22.
W=
(1)
7fr~
where
(2)
R=_^!!.
is
first
known
as the
to notice that
spectra.
Rydberg Constant, because Rydberg was the

occurred in the representations of numerous
it
Since
_ wM _ m
M.
**~m+M.~
(3)
1
~
9
depends on the ratio of the electron mass
The
m to
limiting value for infinitely heavy nuclei
the nuclear mass

is
For other atoms
(5)
1+
The correction
w/M=l/1830
factor
is
m
M
here very nearly
1,
since even for
in the majority of cases, therefore,
hydrogen
R may, to a suffi-
cient approximation, be replaced by R^.

Spectroscopists prefer to specify spectral lines not in frequencies
but in wave numbers, i.e. number of waves per cm.
will follow
We
the usual notation and write v for the

in
23-29.
wave number
of a line or
for the mechanical frequency in an orbit.

The wave numbers of the spectral lines corresponding to the
(l)are
term
This should not be confused with the earlier use of v
terms

v
(6)
= I (WW - WW) =RZ

Ac
149
-L - -I
'
\n a
According to the correspondence principle all transitions between

the stationary states occur, since in the Fourier series for the motion
22, the coefficients of all the harmonics differ from zero.
(26),
Z=l
the spectrum of the hydrogen atom is obtained from

equation (6), and, for n 2 2, in particular, the long-familiar Balmer
For
series
The strongest support of the Bohr theory consists in the agreement

of the quantity
n determined from the spectroscopic measure-
ments
of this series, with that expressed

atomic constants (the difference between
by
(4)
and
R H and R x
(5),
is
in terms of
smaller than
the relative errors of measurement of the atomic constants).

According to deviation experiments on cathode rays
m
by
Millikan's
measurement
gm.
of the smallest charge
e-4-77
on a drop
10- 10 E.S.U.,
according to heat radiation measurements and determinations of the

limit of the continuous X-ray spectrum (see later)
h ==6-54
10~ 27 erg sec
with these numerical values one finds from
cR=3-28
(4)
10 15 sec- 1 ,
R^l-Og.lOScm- 1
the value deduced directly from the observed spectrum
R H =109678 cmThe agreement
of the
is
1
.
two numbers lies within the limits of accuracy

from (4) using the observed values of e, e/m,
in the value calculated
and
h.
This gives for the work done in separating the electron

the one-quantum orbit
=-cRA=2-15
when
in
10- 11 erg.
This value can also be expressed in kilocalories per gram molecule

23
by multiplying by Avogadro's number N=6-0^ 10 and dividing
.
10
by the mechanical equivalent of heat 4-18 X 10 ergs per kcal. The
result is 312 kcal. Finally, as a measure of the energy, use is often.
150
made of the
V in volts through which an electron must pass
potential
in order to gain the
energy under consideration
we have
eV
w- 300'
The value 13-53 volts is found for the energy of the hydrogen electron.
The general transformation formula is
-kcal.
(7)
volt=23-0
- =-1-59
gm. mol.
10- 12 erg=8-ll
which is directly
It is the potential
electron impact (see Introduction,
3).
The formula
(6) contains, in
following hydrogen
1.
The
series
ultra-violet
measured
10 3
in the
cm- 1
method
of
addition to the Balmer series, the
Lyman
series,
Since the constant term in this series formula corresponds to the

"
"
normal state of the atom, the series occurs in non-excited atomic
hydrogen as an absorption series.

2. The infra-red Paschen series,
For Z
we obtain the spectrum
"
spectrum
to even
of helium).
"
helium (the
spark
In this spectrum the lines which correspond
of ionised
quantum numbers (w=2N),
~
2
N?/'
are situated in close proximity to the hydrogen lines,
This similarity between the spark spectrum of helium and the specof hydrogen was responsible for the fact that the former used
trum
to be written in the form
..
2,
lines, observed in certain stars and nebulae, which fitted

this formula were ascribed to hydrogen. Bohr made the situation
and the

clear
151
and showed that the difference between the two Rydberg conR u and RHo was due to the differences in the nuclear masses
stants
M in
(3).
The
++
hitherto unobserved spectrum of doubly ionised lithium
given by putting Z=3.

In addition to the quantitative agreement of the spectra the
orders of magnitude are also in favour of Bohr's model of the atom.
For the radius of the normal orbit of the hydrogen atom, considered
as a circle, we have by (10),
22, for fj,=m
(Li
is
a**
H = A-4
*
(8)
'
2//i/
,o2
this falls within the order of
=0-532
10~8
magnitude
cm
of estimates
deduced from
the kinetic theory of gases and other atomic theories. For the semimajor axis of the excited hydrogen ellipses we have by (10), 22,
a=aH
(9)
.n2
the radii of the corresponding orbits of

in the ratio 1 2 and 1 3 respectively.
The
Li++ are smaller
24.
He + and
Series
Arrangement of Lines in Spectra not of

the Hydrogen Type
We proceed now to those

we have already mentioned
spectra not of the hydrogen type. As

21 we endeavour, following Bohr,
to ascribe the production of these spectra to transitions between
stationary states of the atom, each of these stationary states being
"
"
or
characterised essentially by the motion of a single
radiating
"
"
electron in an orbit under the influence of the core, which
series
in
represented approximately by a central field of force. This conception explains some of the most important regularities of the
is
namely, the existence of several series, each of

the hydrogen type, and the possithese.
between
of
combinations
bility
In a (non-Coulomb) central field of force the motion depends,
series of spectra,
which
is
more or
less similar to
21, on the subsidiary quantum number k in addition

according to
to the principal quantum number n. k has a simple mechanical
momentum of the electron
significance, being in fact the total angular
measured in units of A/27T.

The Bohr relation between frequencies of radiation and energy
differences of the radiating system,
152
corresponds to the general observation that the regularities which

occur in observed spectra can be expressed by writing the wave
number of a line as the difference of two terms, the number of terms
being less than the number of lines ordered by means of them. In
our simple atomic model the terms depend on two integers n and k
and can therefore be denoted by the symbol n k
We found, by
.
applying the correspondence principle, that only such terms may

combine with one another as have values of k differing by
1
(sec (11'),
With
21).
this theoretically
actually observed.
we compare that
terms of any one spectrum
predicted spectrum
The empirical
set of
l
an indiarranged by spectroscopists in a number of term series
vidual term is denoted by its number in the term series and
by the
is
name
of this series.
The usual designation of these term series is
derived from the historical designation of the corresponding line
s (sharp or second subordinate
series
series), p (principal series),
:
(diffuse or first subordinate series),
(fundamental series, often

sometimes /' or /*), etc.
There is therefore a series of s-terms, one ol p- d- fterms
further, each of these may be multiple, but this possibility we shall
2
disregard for the time being.
called also
6,
Bcrgmann
series),
(called
With the usual spectroscopic numbering

we derive the following scheme
of the
terms in the
series
25
Is
In each of these
series
3s
4s
3d
5s
6s
...
4d
5d
60!
...
4/
5/
6/
the terms with increasing order number de-
crease towards zero.
In order to see
we
how our numbers n and k are related to these letters,
refer to the following observations

respecting the
of the terms.
Under normal conditions
(i.e.
combination
when the atoms
are in
direct interaction with the radiation without

being disturbed
external influences) the following rules hold 3
by
word
"
"
is sometimes used for a term

sequence
series, and the word
then restricted to mean a scries of lines in the spectrum.
2
The multiplicity of the terms cannot be explained on the assumption of a point
electron and a central field of force.
It was first ascribed to a
space quantisation
of the orbit of the radiating electron with
respect to an axis in the core, and later to
a spin of the electron itself (</. p. 155).
Thc^
"
"series
is
3
Thoy are obeyed strictly in the more simply constructed types of spectra, e.g.
those of the alkalies and of Cu and Ag. In the other
spectra also they are for the

Two terms of the same term series never combine.
The only combinations are s- with y-terms, p- with
terms, d- with p- and /-terms, etc.
153
1.
2.
s-
and
d-
From this it is clear that the separate term series differ in the quantum number k and that taking the term series in the order s, p, d,
the number k increases or decreases by 1 from one to the
/
.
Since
next.
sumably
1, 2, 3,
We
represents the end of the series of combinations, preterm series s-, p-, d-,f., k is to be put equal to
in the
4 respectively. 1
shall
now
see
what can be said regarding the magnitudes
of
the terms.
The
field of force of
the core of an
atom
is,
at a sufficiently great
In the case of the neutral atom

distance, a Coulomb, field of force.
"
"
it corresponds to the
effective
nuclear charge Z=l, in the case
of the 1-, 2- ... fold ionised atom Z=2, 3 ... respectively. The
orbits of the radiating electron at a large distance are therefore
similar to those in the case of hydrogen. They differ from the Kepler
ellipses
only by the fact that the perihelion executes a slow rotation

The semi-axes and parameter of the
in the plane of the orbit.

ellipses are,
The
by
(9), (10),
and
perihelion radius vector
(11) of
is
22,
for a fixed value of k this distance lies between 1/2 and I, the exact
value depending on the value of n. The larger the value of k the
more of the orbit is situated in the Coulomb part of the field of
force
for large values of k the terms are consequently similar to
;
those of hydrogen. This confirms the adopted numbering of the

series by the values of k, for observation shows that the terms
most part valid the exceptions point to a deficiency of our model (they may depend
on quantum transitions of the core electrons, or to interactions of the scries electron
with the core which cannot bo represented by a central field).
;
A. Sommcrfeld,
Bay. Akad.
d. Wiss., Math. Phys. C7.,

p. 131, 1916,
Verh. d. Dtsch. Phys. Ges. 9 vol. xxi, p. 240, 1919.
This co-ordination is possible only in those spectra where one electron can be
In the case of more complicated spectra
singled out as the radiating electron.
the designations s- t p- t d- terms must be associated with the resultant
angular
momentum of all the external electrons.
tiitz.-Ber. d.
and A. Sommerfeld and W. Kossel,
154
approximate more and more nearly to those of hydrogen the further

we proceed in the order s, p,d,f....
From the term series the line series are obtained by keeping one
term fixed and allowing the other to traverse a term series. The
most commonly observed series by far, and those which have given
their
names
to the terms, are the following
....
Principal series (H.-S.)

Diffuse (1st subordinate) series
Sharp (2nd subordinate)
(I.
N.-S.)
series (II. N.-S.)
Fundamental (Bergmann)
series (F.-S.)
v=ls
v=2p
mp
md
v2pms
v=3dmf.
In addition to these the following combinations occur
....
.....
v=2s
Second principal series

Second diffuse series
v=Sp
mp
md
v=Sdmp
v4fmd.
Not only these term
differences,
but also the terms themselves,
Thanks to our hypothesis regarding

significance.
the potential energy, which we have supposed to vanish at infinity,
of the energy constant denotes the work which
the magnitude
is necessary to remove an electron from its stationary orbit to infinity
have a physical
and to bring it to rest there (relatively to the nucleus). If the stationary orbit of the electron is that of the normal state, then this work is
the work of ionisation.
1
Also the energies
converge to zero, with increasing n, as in the
case of hydrogen, and further the empirical terms of a single term
series likewise converge to zero, so the energy values ascribed theoreti-
agreement with the empirical terms the wave number of

a term multiplied by he is therefore a measure of the work required
to remove the electron from the orbit to a state of rest at infinity.
The largest existing term corresponds to the orbit of the electron
in the normal state and gives a measure of the ionisation potential.
cally are in
term
an s-term, as
the case for several of the simpler

the frequency of the limit (w=oo )
spectra, the ionisation potential
of the principal series multiplied by h if the largest term is a p-teim,
If this
is
is
is
the ionisation potential is the frequency of the common limit of the

two subordinate series multiplied by h. Simple spectra are also
known for which a d-term corresponds to the normal state (e.g. Sc++).
All that
we can expect
of our simple atomic model,
t
1
of
This result arises from the behaviour of the integral
W tending to zero, when U(r)
by means
of
1/r for r large.
(6),
21, for negative values
155
which we replace the non-mechanical motion of the radiating electron

by a mechanical one based on the assumption of a spherically symmetrical field of force for the core, is that it shall give a rough indication of the general characteristics of the line spectra. As a matter of
fact it makes comprehensible the series arrangement of the lines and
terms as well as the increasing similarity of the higher series to those

of hydrogen. Of the most important remaining unexplained facts we
mention once more the multiplicity of the terms. In all of the alkali
spectra the p-, dare also triple p-, d.
many
terms are double, in the alkaline earths there

terms. Other elements, e.g. Sc, Ti, Va, Cr,
higher multiplicities. We mention further the

elements have term systems of the structure described
Mn, Fe exhibit
fact that
still
here, e.g. the alkaline earths
have a complete system of
single
terms
terms.
as well as a system with single s-terms and triple p-, doccur
to
the
above-mentioned
rule
for
the
change
Finally, exceptions
.
of
in
quantum
transitions.
The
multiplicity may be accounted for in principle by assuming

deviations from the central symmetry of the core. If these deviations
are small, they produce a secular precession of the angular momenvector of the radiating electron and core about the axis of the
tum
momentum of the system. Space quantisation

different energy value becoming associated with
somewhat
a
occurs,
each orientation. But this argument leads to multiplicities which
do not correspond exactly to those observed. 1 Pauli 2 has shown
that these could be explained by ascribing four quantum numbers to
each electron instead of three and to account for the fourth quan-
resultant angular
tum number Uhlenbeck and Goudsmit 3
suggested that the electron

This hypothesis has been very
fruitful for the understanding of spectra with multiple terms, but it
will not be considered in this volume.
had a quantised spin about an
25.
We
axis.
Estimation of the Energy Values of Outer Orbits in

Spectra not of the Hydrogen Type
found that the orbit
of the radiating electron

is situated in an
like for large values of k, since it
Coulomb
field of force.
For smaller values
of
was hydrogen-
approximately
k the orbit approaches
1
For multiplicities and Zeeman effects cf. E. Back and A. Lande, Zeetrtanejfekt
und MuUipkttetruktur der Spektrallinien, Berlin, Julius Springer, 1925, vol. i of
the German series, Rtruktur der Matene and K Hurid, Linienspektra vol. iv of the
same series.
t
'
W. Pauli, Zeitschr. f. Physik, vol. xxxi, p. 765, 1925.

3
G. E. Uhlenbeck and S. Goudsmit, Natunvissenschaften, vol. xiii, p. 953,
Nature, vol. cxvii, p. 264, 1926.
2
1925;
156
the region of the core electrons.
As long
be permissible, to a
as
it
does not penetrate
approximation, to expand
the potential energy of the central field of force in powers of 1/r when
1
We write
calculating the value of a term.
this region it will
first
where a denotes a length which may conveniently be put equal to

an (see (8), 23). The radial action integral is then, by (4), 21
:
B C
-11
where
D-
2
2
+-2we Za I[ c 2
We assume now
that in the, expansion for U(r ) the term quadratic in

small in comparison with the linear term, and calculate as a
first approximation the influence of the subsidiary term c xa/r in the
potential energy on the value of the term. This calculation may be
a jr
is
carried out rigorously for all values of c v The phase integral has the
in 22, and we obtain by complex integration (cf. (5),
same form as
Appendix
II)
B
and from
this
A
we
If
substitute for
constant
R from
B and C their values

23,
(2),
we
and introduce the Rydberg
get
(2)
(2)
where
(using
only,
1
(8),
we can
23).
If
write
the deviation from the Coulomb field
is
small
See A. Sommerfeld, Atomic Structure and Spectral Lines (Methuen), p. 596.
157
(3,
The
influence of the additional
value of the term
term
may
--w*-^2
-pr
written in the form
in the potential energy
be expressed as follows
2
the
"
effective
If
on the
the energy be
"
quantum number w*
from the integral value n, which it has for hydrogen, by a

amount 8. The difference depends on k, but not on n, and its
amount will be smaller the larger the value of k. The deviation
from the Coulomb field, caused by the core electrons, will consist
mainly of a more rapid variation of the potential with r, since as
differs
small
r decreases the attractive action of the highly charged nucleus will

be less and less weakened by the core electrons. Assuming that the
first
term
of the expansion is the determining factor, this means that

is
positive. 8 is then negative, so that we
in our expansion (1) c t
should expect the magnitude n*, the effective quantum number, to

be smaller than n.
The form of the orbit is, as in every multiply-periodic central
motion, a rosette. Its equation is easily found. In order to derive
we again
it
By (12),
21,
introduce the co-ordinates
r,
if;
in the orbital plane.
we obtain then for the differential equation of the orbit
_
or
dr
A2
2B
if
^2
_j
^y
The equation has almost the same form as in the case

A and B have the same meaning as there
motion
A=2M (-W),
C
is
somewhat
of the Kepler
different
and y has the value
r
The
integration of the equation (4)
is
carried out in precisely the
158
same way
as in the case of the Kepler motion,
and leads to
(cf.
22)
C
9*=
B+ VfiSwe
If
we
introduce here the abbreviations
(cf. (6),
22)
get
r
(6)
l+
COS y(*A
ô)
The equation of the path differs from that of an ellipse with the
parameter I and eccentricity e by the factor y. While r goes through
one libration, the true anomaly
increases by 2?r/y. The path approaches more nearly to an ellipse the smaller the coefficient c x of
the additional term in the potential energy, and for c 1 =0 it becomes
an ellipse. For small values of c l we can regard the path as an
ellipse,
whose perihelion slowly rotates with the angular velocity

\y
mean motion
of the point on the ellipse.

take into account the term c 2 (a/r) 2 in (1), but only in the
case where its influence is small. We find then by complex integraco 1 is
here the
We now
tion
(cf. (10),
and from
Appendix
II)
this
A=-2mW
and
where this time

(7)
S=-
BD
159
The following term c3 (a/r) may be taken into account in a similar

way and would lead to a dependence of the quantity 8 on n in the
form
However, we
instead,
we
shall
not carry out the calculation in this
will again calculate the influence of the additional
way
terms
in the potential energy, this time with the help of the method of
18.
The result will be of less generality
secular perturbations,
only inasmuch as we must suppose the quantity c t to be small as
well as c a c 3
where
is
We
write
the Hamiltonian function of the Kepler motion, con-
sequently
H-WHO
oand we regard
as the perturbation function.
The unperturbed motion is doubly de-
the perturbation makes it singly degenerate. We obtain

generate
the secular motion of the angle variables now no longer degenerate,
and the influence of the perturbation on the energy, by averaging H l
;
over the unperturbed motion.
In this way we find
The mean values are by
22
(19),
_1_
Z*
""06"
Z*
_
V>
42oH5n3
7
ife
160
On
introducing the Rydberg constant
2a Hhc
we
get
W=-
+
+ f!+Ll
nk*
nlc?
2 )c 4
nF
Writing
W in the form
W=-~
~,
n*
(9)}
v
we
find,
on neglecting products
of the c/s,
or
"*=n+8 1 +??+
(11)
where
1=
Zcj
Z 2c 2
3Z 3c 3
""^"""
5Z 4c 4
We now compare these theoretical formulae with observation.

The terms derived from observations of spectra of the non-hydrogen
type
may
in fact be written in the
RZ
form
on n. Rydberg 1 was the

first to suggest this form and verified it by measurements of numerous
where, in general, 8 depends very
We
spectra.
correction.
shall therefore denote the quantity 8 as the Rydberg

The remaining deviations have been represented by
<
little
R. Rydberg, K. Svenska Akad. HandL, vol. xxiii, 1889

an expansion in
2
1/w equivalent to the Rydberg formula has been given independently by H. Kayser
and C. Runge (Berlin. Akad., 1889 to 1892).
J.

Ritz,
who gave
161
a series expansion for the difference between n* and
the whole number
S=S 1 +8 8 I+...
(12)
Eitz used also the implicit formula
(13)
-??L
The Rydberg-Ritz Formula
26.
The Rydbcrg-Ritz formula can be
established empirically not
only for the terms of the outer orbits, but also for orbits which pene"
trate the core and which we shall call
penetrating orbits." It may
in fact be derived theoretically for very general cases.
show next that for an arbitrary central field the formula
We
RX2
(1)
(n
l-^+S^)
2
corresponds to a reasonable series expansion.
The connection between the quantum numbers and the wave
number
(U(r)
is
v of tho term
negative, sec
is
given by the equation
21.)
We
compare
-2|
hv-
this
(cf. (4),
21
with the expression
which, for the same v, corresponds to a Coulomb field of force.

this n* is of course not an integer, but has the value given by
For
_RZ
n*
The
difference of the
we imagine
it
integrals is a function of v and k alone.

in terms of v and put equal to
two
expanded
If
we obtain
W.
Ritz, Ann. d. Physik, vol. xii, p. 264, 1903 ; Physikal. Zeitschr., vol.
1908 ; see also Ges. Werke, Paris, 1911.
G. Wentzel, Zeitechr. /. Physik, vol. xix, p. 53, 1923.
p. 621,
8
ix,
162
and
RZ 2
Since for larger values of
we can conclude from
n the term
v rapidly approaches zero,
this consideration that the correction
Sj+Sg^
rapidly converges to a fixed limiting value for increasing n.

The following argument due to Bohr, 1 goes much further towards
providing a theoretical basis for the Rydberg-Ritz formula (1), and

gives this formula greater physical significance.
The real object of the introduction of the central field was to
describe,
by means
of a simple model, the (certainly non-mechanical)

and radiating electron, for which no ex-
interaction between core
change of energy between core and electron occurs. Now this

assumption regarding the constancy of the energy of the radiating
electron is alone enough to enable us to deduce the series formula,
this
without special assumptions regarding the field of force
derivation is, in consequence, not only valid for any atom whose
spectrum can be ascribed to a single series electron, but even for
molecules. Certainly molecules do not emit line but band spectra
;
produced chiefly by transitions of a radiating

are
which
on
electron,
superimposed the quantum transitions of the
molecule as a whole from one state of rotational or oscillatory
these, however, are also
motion to another.
Further, this derivation
exchange
of angular
is
altogether independent of whether an

core and electron takes
momentum between
place or not, i.e. whether or not an azimuthal quantum number k

can be defined in a manner analogous to that in the case of central
motion.
The only assumption which we make is that the core (which

includes one nucleus in the case of one atom and several in the case
of a molecule) is small in comparison with the dimensions of the
path of the radiating electron. The field will then closely resemble
over most of the path outside the core the distance

from
the centre point of the core will be determined
of the aphelion
only by the potential energy in the aphelion, it is therefore equal
for all loops of the path independently of whether these loops are
similar to one another (as for a central field) or not. Accordingly
an effective quantum number n* may be so defined that the relation
a Coulomb
We
field
are indebted to Professor
Bohr
for kindly
which the following paragraphs are based.
communicating the ideas on
163
is valid in the Coulomb field, between n* and aphelion

and energy respectively
dRAZ 2
holds which
distance
We
that
assume, on account of the periodicity of the electron motion,

is then a function of
it has a principal quantum number n
motion
for the radial period r of the
aphelion to aphelion)
(
J=wA, and
(i.e.
the time from
we have
'
The radial period T*

same energy (2) is
==
dJ
of the
h 8n'
motion in the Kepler
ellipse
with the
(4)
v
'
In a single term series we consider the variation of energy with

the principal action integral J or principal quantum number n, for
constant values of the other quantum numbers for such a variation
;
we may invert
the derivatives
and
(3)
(4),
and
find for a
term
series
'
Now
(2),
the Rydberg correction 8

is he times the
25), and
term in the spectrum, so that
is
equal to n*
n (compare
(2)
with
wave number
for a
v of the corresponding
series
term
=**->
(5)
The
radial
motion in the two orbits
is
only different over that
part of the actual orbit where the field of the core is appreciable
the proportion of a radial period spent in this part of the orbit is
small, if the core is small compared to the dimensions of the orbit
;
of the series electron as assumed, so r*

If it
T
can be taken to have a constant value
is
small compared to
r.
T *_ T= 8 2/c
over the range of v covered by the term
series, (5) integrates directly
to
8
= 8 1+ 8
2 v,
whence the Ritz formula
(1) follows at once.

t
If T*
T cannot be taken as constant, it seems probable that it
will be expansible in a power series in
or v (this can certainly be
164
done
if
power
the
field is central)
series in v
the
"
integration of (5) then gives 8 as a
extended Kitz formula."
In order to provide a survey of the validity of this formula we

give the values of the effective quantum number n* for the terms
of two typical spectra, those of Na and Al
:
Na.
2-64
1-63
2-12
P
d
4-65
3-65
3-13
2-99
4-14
3-99
4-00
4-99
5-00
Al
219
d
4-23
3-22
2-67
2-63
1-51
3-70
3-42
5-23
4-26
3-97
6-23
5-72
4-71
5-16
4-96
6-11
7-08 8-07
5-96
The Na-spectrum and the s- p-, and /-scries of the Al-spectrum

show the behaviour which we find for almost all term series, namely,
on the term
very little dependence of the Kydberg correction
number n. The d-series of aluminium and a few other known series
form the exception, inasmuch as the limiting value of the correction
is reached only for comparatively high term number.
Since, for the time being, we do not know the quantum number
n only the fractional part of 8 can yet be found, the integer is un9
n*n
determined. If we choose the integers here so that the magnitudes

of 8 decrease with increasing k and at the same time are as small as
possible, we obtain as limiting values for large n
:
N.a
Al
Now
1-35
1-77
-0-80
-1-28
-0-01
-
0-93
0-00
-004
25 were applicable, |S| would increase as

the analysis of
5
or
(JO),
25), as k decreased and the orbit at
(cf.
1/F
I/A:
closer
to
came
the
nucleus
it will be seen from these
perihelion
if
l/k or
examples, and from all other series spectra, that there comes a stage
at which the increase of |8| with decreasing k is very much more
rapid than that given by any of these inverse powers. The large
values of 8 show us, moreover, that we can no longer regard it as a
small correction of n.
The
large deviations of the term values from the hydrogen terms

be
may
explained if we consider that the orbit of the series electron
is not
always situated entirely outside the core, even in the excited

but penetrates into
states,
is
of the nucleus
Coulomb
Such a penetrating orbit (Tauchbahn)
it.
much more strongly
in its innermost parts
with a higher nuclear charge. Under such

25, for the potential energy will not be
field of force
conditions use of
subject to the influence
therefore, a field of force similar to a
it traverses,
165
(1),
justified.
In the case of
of the 8-values
Na
a noticeable irregularity
between the d- and y-terms
is
;
d-orbits are situated entirely outside the core

y-orbits penetrate into the core.
27.
The Rydberg Corrections
and that the
of the Outer Orbits
Polarisation of the
We now
present in the course
this suggests that the

s-
and
and the
Atomic Core
consider in greater detail the physical influences which

field of force outside the core from a Coulomb
cause a departure of the

field of force. 1
of a/r
First
we can determine approximately which power
especially important in the potential.

in
the form
energy
is
We write the
orbital
cRAZ 2
w_
'^+5
2*7
An
additional term
(10),
and a
An
25, a
"
"
in the potential energy gives
cl
Rydberg correction
Ritz correction
e2
additional term
--Z
a
.
r2
gives
~\
an additional term
1
by
"
--Z
e
a
.
S 2 =0;
c3 -^- gives
M. Born and W. Heisenberg, Zeitschr. f Physik, vol. xxiii, p. 388, 1924 ; the
numerical values of the following tables are taken from this work. For further
work on this subject, see D. R. Hartree, Proc. Roy. ti<9b. t vol. cvi, p. 552, 1924;
E. Schrodinger, Ann. d. Physik, vol. Ixxvii,
p. 43, 1925 ; A. Unsold, Zeitschr. f.
Phyaik, vol. xxxvi, p. 92, 1926 ; B. Swirles, Proc. Camb. Phil Soc., vol. xxiii, p. 403,
1926*
166
s
o
2
-,
and an additional term
CA
*r4
5
5J
1-
Z4c 4*
A;
82
'
_ Z3c
;rr^>
3
S2
~
__P
i?9
gives
= 3Zc
The following table gives the values of the Rydberg and Ritz
corrections and their ratio, determined from the spectra of the alkali
metals, whose structure is especially simple.
The
letter
in the table denotes that the
Rydberg correction
is
too
large so that an expansion of the potential in powers of l/r does not
appear
justifiable.
The
Sg/Sj^ shows that the higher powers of l/r are

large value of
present in the potential to an appreciable extent. For the terms with
c3 /r 4
and cjr5 we obtain theoretically the values
From
this it appears that the
term containing
c 3 /r 4 is the essential
additional term.
Now such an additional term in the potential energy has in fact a

theoretical significance. For if the core of the atom, instead of being
regarded as absolutely rigid, is considered to be capable of deformation, it will acquire an electric moment in the field of the series elecIf the electron is at a sufficient distance from the core, the
tron.
field
=e/r produced by
sidered as homogeneous.
it
in the vicinity of the core may be conof the core is pro-
The induced moment
167
p = aefr The moment of such a doublet

an
electric
field
in its neighbourhood
if it be considered
produces
to arise from the approach of two charges p/l at a distance I apart it
will be seen that the force exerted on the radiating electron, in the
2
portional to this field:
direction of its axis, will be
pel
Its potential is
field
ae 2 /2r 4
At
"_
1\
2pe_2ae*
If the other deviations
from the Coulomb
be neglected, we have
2Za [t 3
and
3
Z2a
Our assumption, that the departure of the field of force from a

Coulomb field is due essentially to the induced doublet in the core,
may
be tested by calculating the
"
"
polarisability
a,
from the
empirical values of 8 l and 8 2 It must be assumed that the cores of

the alkalies Li, Na, K, Kb, Cs are vsimilar in structure to the neiitral
.
same number of electrons)

The
values of a for these atoms
30).
constants
be
from
dielectric
between them and
determined
the
may
atoms
of the inert gases (containing the
He, Ne, A, Kr, X (see further,
the a- values of the alkali cores a simple relation should exist.

From the empirical 8 ^ values of the alkalies we get
Li+
Na+
K+
Rb+
O+
0-314
0-405
1-68
..
6-48
a-10 24 -
For this the /-terms are used with the exception of Li, the j9-term of
which serves for the calculations Rb is omitted on account of its
somewhat anomalous Rydberg and Ritz correction. The polaris;
the inert gases are related to the dielectric constants

or with the refractive indices n for infinitely long waves by the
abilities of
Lorentz-Lorenz formula
3
-l
n 2 -!
where N is the number of atoms per unit volume. If the optically

measured refractive indices be extrapolated for infinitely long waves,
one finds
.
A
Kr
Ne
X
He
|
a-10 24 =
0-20
0-39
1-63
2-46
4-00
168
The a- values of the alkali ions must be somewhat smaller since the
volumes of the ions must be less than those of the preceding inert
gas atoms on account of the higher nuclear charge.
We find consequently that the a- values calculated from the spectrum have the right order
too large. One might be
of magnitude, but that they are all rather

inclined to account for the difference by
assuming that, in addition to the induced moment, still another

deviation from the Coulomb law of force is present, likewise corre4
We
sponding to an auxiliary term of the approximate form c 3 /r
cannot at this point prove whether such an assumption is admissible.
It should, however, be mentioned that our knowledge of the structure
of the ions of the inert gas type hardly admits of such a possibility.
.
If the
explanation given here of the Rydberg correction as being
due to polarisation of the core be retained, then a contradiction remains which, from the standpoint of our quantum rules, cannot be
removed. We have, however, already referred to the fact that the
explanation of the finer details of the spectra (the multiplets and the
closely allied anomalous Zeeinan effect) does not appear possible
within the range of a quantum theory of multiply-periodic systems.
One is led by the theory of these phenomena to the formal remedy of
giving to the quantum number k half integral values, i.e. to give it
the values
J,
fj,
etc.
It
is
to be expected that in the further
development of the theory the real quantum numbers will remain

integral as before and that the quantity k, occurring in our approximate theory, is not itself such a quantum magnitude, but is built
up indirectly out of them. We shall not go into these questions in
the present book we shall content ourselves with seeing what values
are obtained for a when we choose half values for k in our formula.
We find, then, from the spectroscopic values of S, the following
;
a- values
Li+
Na<
K+
0-075
0-21
0-87
Rb+
Cs+
-1C 24
3-36
..
These numbers are related in the right sense to the a-values of the
This connection can be traced still further by considering
inert gases.
the a-values of other (multiple- valued) ions of inert gas type, which
may be determined partly from the Rydberg corrections of spectra
of the ionised element (spark spectra), partly from the refractive
indices of solid salts, (ionic lattice). In this way further support is
obtained for the view that the Rydberg correction of the terms of
the outer orbits in the spectra under consideration
is
due to the

polarisation of the atomic core
to be given half values. 1
The
169
and that the quantum number
Jc
is
investigations dealt with in this volume are otherwise indefor whole or half values for k.
pendent of a decision
The Penetrating
28.
Orbits
26 we have ascribed the large values of the Rydberg corrections to the fact that the electron penetrates deeply into the atomic
In
and
is thus subjected to an increased nuclear influence.

estimate of the orders of magnitude to be expected for the 8"
"
values for such penetrating orbits may be obtained by a procedure
due to E. Schrodinger. 2 He considers the core of the atom replaced by
core,
An
a spherical shell uniformly charged with negative electricity, external

to which there is then a Coulomb
corresponding to the
nuclear charge Z (a) (1 for a neutral,
2 for a singly ionised atom), and in
field of force,
the interior of which there

wise a Coulomb
field,
is
like
but corre-
sponding to a higher nuclear charge

Z(l)
As soon as the perihelion
.
distance of a
quantum
orbit, cal-
culated as an ellipse in the field of force with the nuclear charge

Z(rt) becomes smaller than the radius of this spherical shell, the orbit
penetrates into the interior it consists then of two elliptic arcs which
,
join smoothly at the intersection with the spherical shell
(fig. 14).
For given quantum numbers n and fc, given shell radius, and given
charges of the shell and nucleus, the effective quantum number n*
or the correction 8
We
show
may
be calculated.
shall not repeat Schrodinger's calculations here

only that by means of such an atomic model, which
we
shall
may even
consist of several concentric shells with surface charges, the relation

between quantum numbers and energy may be expressed in terms of
1
This evidence is by no moans conclusive, since values of the polarisability a
deduced from terms of spectra corresponding to external orbits depend to a consideiable extent on the term series from which they are deduced, so conclusions
drawn from comparison of values of a deduced from a single series with values
deduced from other phenomena must be regarded with caution. We may also
mention here that the polarising field on the core due to an electron in an orbit
radius 9 H (the radius of the 3-quantum circular orbit of hydrogen) is about 10 8
times the field in strong sunlight, and the displacement of the electrons in the core
polarised by this field may be an appreciable fraction of the core radius.
2
E. Schrodinger, Zeitschr.
f.
Physik, vol. iv, p. 347, 1921.
170
1
Let the shell radii be p l9 p 2
arranged in
elementary functions.
of
and
their
z 2e ....
order
ztf,
charges
magnitude,
decreasing
The potential energy in the space between the shells p s and ps+1 is
>
where
and
determined by the condition that at the

It follows from this that
c 8 is
shells the potential
varies continuously.
îPcr
the potential energy as a function of r, we can
calculate the perihelion distance r min and state within which shells
we now know
Since
p l9 p 2
(4),
pp
21, the
it lies.
The
radial action integral has, according to
form
Bn
where
All the integrals may be expressed in terms of elementary functions ;

and k,
in this way we obtain J r and hence (w k) as a function of
and
finally W as a function of n and
k.
2
Following van Urk we shall make use of Schrodinger's conception
of the charged shells to estimate the 8-values for the penetrating
orbits. It will be seen that the larger the radius of the spherical
be the radial action integral, for a given external

for the larger this radius, the longer will the electron move
shell the larger will

ellipse
1
Cf. also G.
Wentzel, Zeitschr. f. Physik, vol. xix, p. 53, 1923, especially p. 55.

A. Th. van Urk, Zeitechr. f. Physik, vol. xiii, p. 268, 1923.
SYSTEMS WITH ONE RAMATING ELECTRON
171
under the influence of the full nuclear charge. One obtains, therefore, from the Schrodinger model, on the assumption that an orbit
of the penetrating kind, a lower limit for the magnitude of 8
by choosing the radius of the shell so that it touches the external
is
If
ellipse.
we wish to find the value to which
8 tends for large values

of the
on n is extremely small in the case

we
can take as the perihelion distance
Schrodinger model),
of
(the dependence
external ellipse that of the parabola

fore, 5^7-)%,
we
of the
in the case of the s-orbit, there-
shall write generally
^f\i-
Since
we choose
the
radius of the sphere equally large, the total orbit of the radiating
electron will be given to a close approximation by the two complete
ellipses.
We get for the radial action integral

J r __j r()_|_J
u
u r(0
\
>
(a) indicating the contribution from the part of the orbit

outside the core, and affix (i) the contribution from the part inside.
affix
Now
is
proportional to the work of separation
and consequently equal to the energy of the
the spectrum term
of the outer electron,
outer ellipse
where J^
ellipses.
is 2?r
If
times the
we compare
common
this
angular
with the form
W=for the energy,
we
momentum
for the
two
n *2
find for the effective
quantum number
But
J r +J t =n
so that
(1)
=M
< l)
=*-n=-^
n
where J is the sum of the action integrals for the inner ellipse.
is determined by the semi-major axis a of the inner
ellipse
(t)
J(0
172
a
is
further related to the radius of the shell
where
a and
If
be eliminated from these three equations
we
find
J(f)
and from
this,
by solving
8=
(2)
and substituting
for
(1) is also
+k.
'
The equation
in (1)
T~m~f
7'^
approximately valid
if
the outer ellipse
cuts the shell at a small angle instead of touching it, so long as the
shell radius is small in comparison with the major axis of the outer
(which
ellipse
is
certainly the case for large values of the principal
(a)
The
quantum number) and if TP^ is considerably greater than Z
error which is then made in replacing the action integral over the
.
outer portion of the orbit by that over the complete outer ellipse is
likewise the error made in replacing the inner portion
then small
the aphelion of the inner ellipse is

ellipse
situated only slightly outside the shell (on account of the rapid
decrease of the potential energy in the field with the nuclear charge
by the complete inner
Z(l) ).
The sum J(t)
of the action integrals of the inner ellipse is
determined uniquely by the major axis of this ellipse, and is consequently almost independent of n.
In the approximation given by formula (1) 8 is not dependent on
This approximation is better the larger the major axis of the outer
since that is rapidly attained by increasing n, we see how 8
ellipse
n.
very soon assumes a constant value with increasing n.

If there are quantum paths which are contained completely in
the interior of the
shell,
and
if
is
the largest of them, then
_h
J<
n(0<
and
the principal
quantum number of

S
(3)
= -(w
(t)
173
0<<1.
+e-fc)
This formula is essentially independent of the Schrodinger model

of the charged spherical shells, and depends only on the fact that the
aphelion distance of the outer orbit is large in comparison with the
core radius, and that the electron penetrating the core soon comes
*
into the region of higher effective nuclear charges. Bohr derived
before v. Urk, in the following way

radial action integral J r =h(n k) of the orbit
the outer portion of the orbit and of the inner loop
:
it,
The
is
composed
of
is only slightly smaller than the radial action integral A(n*

of the complete external ellipse
J/a)
k)
J^^n*-*--*!),
and Jr
(t)
differs
but
little
from the radial action integral
the largest orbit completely contained in the core
h(n^k)
of
is not necessary here that n^ should be integral, but it is the sum

of the action integrals of the largest possible mechanical (not quantum) orbit divided by h. One obtains consequently
It
8=n*-n=-(nW-/j- 1 +,)
(4)
and the result may be formulated as follows

The Rydberg correction for penetrating orbits is not very different 2
from the radial action integral of the largest orbit, completely con:
tained in the core, divided by h.

The question as to the accuracy with which
all optical (and X-ray)

be consistently represented by a suitable central field
has been examined by E. Fues 3 he arrived at eminently satisfactory results in the case of the arc spectrum of Na and the analogous
+
++
spark spectra of Mg and Al
terms
may
29.
The
The X-ray Spectra
optical series spectra of the elements provide one of the

means of obtaining information regarding the structure of
principal
1
Bohr, N., Lectures at Gottingen, June 1922 (unpublished).

In practice, e l e a is no * always small compared to 1 comparison with observed
spectra shows it may be greater than J.
3
E. Fues, Zeitschr. f. Physik, vol. xi, p. 364 vol. xii, pp. 1, 314
vol. xiii, p. 211,
1923 vol. xxi, p. 265, 1924. See also W. Thomas, Zeitschr. f. Physik, vol. xxiv,
on
orbits,
further
work
For
penetrating
especially the relations
p. 169, 1924.
between corresponding terms of different atoms of the same electronic structure,
see E. Fues, Ann. d. Physik, vol. Ixxvi, p. 299, 1924
D. R. Hartree, toe. cit.,
and Proc. Camb. Phil. Soc., vol. xxiii, p. 304, 1926.
2
174
atoms.
In as far as they can be comprehended on the basis of our
theoretical conceptions we can draw conclusions regarding the processes taking place in the exterior portions of atoms only ; they
no information about those occurring in the

inner regions. The most important means of investigating the
internal structure of the atom is the study of the X-ray spectra.
Our theory of the motion of an electron in a central field of force is
afford us little or
applicable also to these, since it may be inferred from the observations that we are here concerned with quantum transitions of the
atom
in
which one electron (corresponding to the
series electron
in the optical spectra) changes its position in the interior of the

atom while the rest of the atom remains approximately a structure
possessing central symmetry.

Before we follow out these ideas in detail, we shall give a brief
summary of some of the results of observations on X-ray spectra.
Since the discovery of v. Laue, the natural gratings of crystals have

for the analysis of these spectra.
Each X-ray spectrum consists of a continuous band and a series of lines.
been available
The continuous spectrum has a short-wave

înax
s rp ' a ted to
limit,
whose frequency
the kinetic energy of the generating cathode rays
by the equation
*"= m2 V
._
This result can be looked upon as a kind of converse to the photoon the assumption that the incident cathode rays are
electric effect,
retarded in the anti-cathode and that their energy
is
transformed
the highest freinto radiation according to the Einstein law ( 2)

of
emitted
then
to
the
total
loss
kinetic energy
corresponds
quency
;
of the incident electrons.
and is
most
The
called, therefore,
important
fact relating to it is that every element exhibits the same arrangement of lines, and that with increasing atomic number the lines
The
line
spectrum
"
characteristic of the radiating matter,
is
characteristic radiation."
towards the shorter wave-lengths. This line spectrum contains

a short-wave group (called K-radiation) has
found
in
the
case of the light elements (from elements
been
already
shift
various groups of lines

in the neighbourhood
Na and
These become continually

and are followed by a group of
onwards).
shorter for the heavier elements,
longer waves (L-radiation) ; behind this group follows, in the case

of still heavier elements, a group of still longer wave-lengths (Mradiation).
175
If these spectral lines are to be related to the motions of the

electrons in the atom in accordance with the principles of the quan-
tum
theory, the X-ray frequencies must be given in terms of the

energies of two stationary electron configurations by the equation
The
large values of v (about 1000 times as great as in the visible

spectrum) indicate that we have to do with variations in the orbits
on account of the high nuclear charge, a

work must be expended in the displacement of an
of the inner electrons where,
amount
large
electron.
of
The
may
fact that the X-ray lines are arranged in simple series, and
be characterised by small integers, forms the ground for the
assumption that, as in the case of the simpler optical spectra, we

"
are here concerned principally with the motion of a single
radiating
Although we arc compelled to assume that
electron."
moves
in the interior of the
this electron
atom we
shall replace the action of the

for
reasons analogous to those
electrons,
nucleus and remaining

holding in the case of the visible spectra, by a central symmetrical
field of force.
By so doing we express once again the fact that no
of
exchange
energy takes place between the radiating electron and
the remainder of the atom
the existence of
for the radiating electron points to its
quantum numbers
motion being periodic, and
assuming, therefore, the same energy after each revolution.

There is, however, a fundamental difference between the optical
spectra and the X-ray spectra. Whereas the lines of the optical
spectra can occur also in absorption, the
observed
lines are
never
absorption
lines.
X-ray
as
The absorption coefficient for

Rontgen rays exhibits, in fact,
no maxima
produces
of the kind
absorption
which
lines
it
shows rather a continuous variation, broken only at certain

places
by the
so-called
"
Fia. 15.
ab-
sorption edges," at which a sudden increase in absorption coefficient

occurs if the frequency is increased through them (fig. 15).
1
explanation of this phenomenon has been given by Kossel.
are
concerned
with
the
the
to
him,
absorption spectra
According
An
j
1
and
W. Kossel, Verhandl d. Ditch, physikal. Ges., vol. xvi, pp. 899

vol. xviii, p. 339, 1916.
and 953, 1914,
176
atom in such a way that an inner electron is removed.

The frequency condition gives for this process
ionisation of the
where v is the velocity of the electron after separation and

is
the work of separation. It follows then that all frequencies will
be absorbed which are greater than the limiting frequency
which
will thus
be the frequency of the absorption edge. The hyatom there are electrons with various different
pothesis that in the
leads then to a variation of the absorption

binding energies
with frequency in qualitative agreement with observation.
According to Kossel the emission lines are caused by an electron
from a higher quantum orbit to replace the ejected electron,

the
whereby
energy of the atom decreases. Further, an electron from
a still higher quantum orbit can fall into the vacated place until
falling in
gap will be filled by a free electron.

The emission spectra of the X-rays arise then from the re-establishment of a stable state of the atom after its disturbance through the
finally the last
an inner electron.
can express this hypothesis of KossePs, which has been comFor every system of quantum numbers,
pletely verified, as follows
ejection of
We
corresponding to inner orbits, there corresponds a maximum number

of electrons. This is reached in the stable state. An exchange of
place occurs, however, when an electron is removed from its inner
All electrons which possess the same quantum numbers are
orbit.
considered as together forming a shell
we
shall
be led subsequently,
by altogether different considerations, principally from the domain

of chemistry, to the same conception of a shell-like structure of atoms
We shall now
endeavour to establish the truth of these confrom

the
quantitative standpoint.
ceptions
Our model, in which the electron under consideration moves in a
central field, gives rosettes for the electron paths, and these are
determined by two quantum numbers n and k. Orbits with different
(
30).
values of
n must
in fact occur in the interior of the atom.
The
behaviour of the Rydberg corrections shows that, for almost all

in order that this may be possible
elements, the p-orbit^ penetrate
;
the core must at least contain orbits with
the core those with
n\
n=2. Of the
orbits in
(&=1) are nearest to the nucleus, then
SYSTEMS WITH ONtl

follow those with
n=2 (k=l
2),
RAM vr ENO
177
ELECTBOTST
'
and then perhaps come
orbits with
n=3
(k=l, 2, 3).
In the elements of high atomic number the innermost orbits are
subject mainly to the attractive force of the nucleus, while the influence of the remaining electrons is comparatively small. The energy
of the innermost electron orbit is then given approximately by
1 and Z equal to the atomic number

as we proceed outwards the energy decreases rapidly, partly on account of the decrease
of n and also on account of the shielding of the nuclear charge by
with n
the remaining electrons.
expected
The wave number
of the first line to be
is
,=
(1)
approximately. The formula requires that Vv shall increase

1
linearly with the nuclear charge. Moseley, who was the first to
study the X-ray spectra systematically, found that for the K-series
Vv is actually very nearly a linear function of the atomic number
by atomic number is understood the number expressing the position
;
an atom
of
3 Li
in the series order of the periodic
system
(1
H, 2 He,
thus practically in the order of the atomic weights

the
gaps required by chemistry (e.g. that of the element 43 homologous
to manganese) are to be taken into account as well as the reversals
.
.),
required by chemical behaviour
[e.g.
18
(at.
wt. 39-88),
and 19
(39-10)].
This provides an excellent verification of the already long-inferred

first put forward by van den Brock
3, p. 13), that
(cf.
principle
2
equal to the number of the nuclear charges.
This enables us also to determine uniquely the atomic numbers of
the atomic
number
is
elements with very high atomic weights, among which occur long series
of elements differing very little chemically from one another (e.g.
the rare earths), and also to determine accurately the existing gaps.
In order to show the accuracy with which the law

give the values of
for
(1) holds,
we
some elements.
o ri
H. 0. J. Mofleley, Phil Mag., vol. xxvi, p. 1024, 1913 ; vol. xxvii, p. 703, 1914.
Strictly speaking, Moseley's law only confirms tha*; the difference between
the atomic number and nuclear charge is the same for all elements whose X-ray
spectrum has been observed ; it does not show that this constant difference is
2
necessarily zero.
12
178
For Na(Z=ll) the value
W(Z=74)
We
it is 76-5.
is
10-1, for
Rb(Z=37)
it is
36-3,
and
for
associate therefore the first K-line with
the transition of an electron from a two-quantum to a one-quantum

orbit.
This suggests associating the remaining K-lines with transitions from higher quantiim orbits to a one-quantum orbit.
K-lines have actually the theoretically required limit
The
RZ 2
T
Situated at the same place
is
one
'
of the
above-mentioned absorption
edges.
Vv
The
We
is valid also for the L-lines.

principle of linear increase of
attempt to identify these lines as transitions to a two-quantum
orbit
(ft
=2), and obtain for one of the L-lines the approximate
wave number
This formula does not hold so well as
we can understand
nucleus.
We
since here
we
it
does for the K-series
this
are at a greater distance from the
can take account of this quantitatively, 1 by writing
(3)
the empirical values are then in agreement with a value for s which,
for medium values of Z, lies
approximately between 6 or 7.
Here again the series limit coincides with an absorption edge. The
M-lines correspond finally to transitions to a
three-quantum orbit.
obtain a clearer survey of the stationary orbits of the electrons in
the atom if from the system of the
X-ray lines we proceed to that of
the X-ray terms. The end term of the K-lines we call the K-term,
We
absorption edge, and corresponding to it

1.
In order to
1, it
account for the multiplicity of the L-lines we must assume three
corresponds to the
our model) are the
it
(in
quantum numbers w
end terms (L-terms) for which w=2 and Jc=l or 2. The fact that
three terms exist instead of two implies that the
quantum numbers
n and k are not
sufficient to define
by a phenomenon very
the optical terms.
On
we
the basis of our model
explanation of this phenomenon. 2

1
them
are confronted here
closely allied to that of the multiplicity of
we cannot
give an
Again, investigations of the
A. Sommerfeld, Anil. d. Physik, vol. li,

125, 1916.
A satisfactory interpretation in terms ofp.the " spinning electron " can be given,
as for the multiplets of
optical spectra (cf. p. 155 and footnote 2, p. 152).
2
FIG. 16.
179
180
X-ray
with
M-terms with w=3 (fc=l, 2, 3), and seven N-terms

some 0-terms have also been established.
lines give
n=4
To provide a survey
of the occurrence of these different terms
we reproduce
here a graphical representation of the terms, taken

from the work of Bohr and Coster * (fig. 16). We find there the K-
and one L-term (w=l, n=2) even for the lightest elements 2 an Mtenn (n=3) appears about the atomic number 21, an N-term (n=4)
about 39, and an 0-term (n=5) at about 51. With regard to the
number of the terms corresponding to each principal quantum number, the resolution into 3, 5, and 7 terms mentioned above is readily
we find first
this resolution occurs in two stages
noticeable
two L-, three M-, and four N-terms, all of which, with the exception
of the first of each, again split up into two terms. If we disregard this
further splitting up, which occurs only for higher atomic numbers,
we have just as many terms as there are values which the subsidiary
quantum number can assume. The rule in accordance with which
the terms combine corresponds exactly to the selection principle for
;
We refer finally to the departures of the square roots of the term

values from a linear variation with the atomic number. These
shown in fig. 1 6, given by Bohr and Coster. The general
curvature of the graphs (especially of that for the K-term) is attri"
"
buted by Sommerfeld 3 to the relativity correction ( 33, p. 201).
are clearly
The small kinks, e.g. at Z=56 and Z 74, are connected, according
Bohr and Coster, with the building up of the inner electron groups,
to a consideration of which we shall shortly return ( 32, p. 191).
to
30.
Atomic Structure and Chemical Properties
The final aim of a theory of atomic structure must be to construct

the whole periodic system of the elements from an atom model. Bohr
had already made attempts in this direction in his earlier works.
He made use of " ring models," in which the individual electrons were
"
situated at the corners of concentric regular polygons (the
rings ").
considerable amount of work has been expended on the calcula-
tions of such ring systems
4
6
8
7
by Bohr, Sommerfeld, Debye, Kroo,
N. Bohr and D. Coster, Zeitschr. f. Physik, vol. xii, p. 342, 1923.

A state of the atom giving another L-term presumably exists for the lighter
elements, but has not been experimentally determined as it is not involved in any
line in the
spectrum, which is the only one of their X-ray spectra yet observed.
3
A. Sommerfeld, Ann. d. Physik, vol. li, p. 125, 1916.
4
N. Bohr, Phil Mcttj., vol. xxvi, p. 476, 1913.
c
A. Sommerfeld, Physical. Zeitschr., vol. xix, p. 297, 1918.
*
P.
J.
Debye, ibid., vol. xviii, p. 276, 1917.

Kroo, ibid., vol. xix, p. 307, 1918.
181
Smekal, and others, particularly with reference to the explanation

of the X-ray spectra ; the results were, however, altogether unsatisfactory. The most important mechanical result arising out of this
was Sommerfeld's observation that such
polygon can not
anêlectron
only rotate about the nucleus, but that it canêxecute a motion in

which the electrons traverse congruent Kepler ellipses (family of
ellipses). Sommerfeld dealt also with the mutual perturbations of
such rings for the case in which they are coplanar as well as for that
which they lie in different planes. Models of this kind have
in
indeed a spatial structure just like the real atoms, but they do not
show the symmetry of the latter as exhibited chemically (e.g. carbon
tetrahedra) as well as crystallographically.
deavoured to construct models with spatial
Lande
therefore en-
symmetry such
that,
common
with Sommerfeld's family of ellipses, the electrons traverse congruent paths in exact phase relations (e.g. simultaneous
in
But these models
passage through the perihelion).

it
came
Bohr
also failed
to quantitative investigations.
realised that, by purely theoretical considerations
when
and the
construction of models, the desired object of explaining the regularities in the structures of atoms (periodic system of the elements)
would be very difficult to attain he therefore adopted a procedure
;
by means
of which, half theoretically
and
half empirically,
making
the evidence provided by physics and chemistry, and,

especially, by a thorough application of the data derived from the
series spectra, there was evolved a picture of the building up of
use of
all
atoms.
The chemical results which are to be taken into account in such

an investigation have been expressed in a suitable form by Kossel. 3
He takes as a starting-point the fact that the periods of the system

of elements begin with an inert gas, the atoms of which are characterised by the fact that they enter into no combinations and can
difficulty. The atoms of the inert gases
stable
are, therefore, particularly
configurations which, perhaps as
a result of the high degree of symmetry, are surrounded only by
be ionised only with extreme
small fields of force and, on account of this great stability, neither

take up electrons easily nor part with them. The atoms preceding
the inert gases are the halogens (F, 01, Br, I) which occur readily
1
A. Smekal, Zeitschr. f. Physik, vol. v, p. 91, 1921.

A. Lande, Verhandl. d. Dtsch, physikal. Ges., vol. xxi, pp. 2, 644, 653, 1919 ;
Zeitschr. f. Physik, vol. ii, pp. 83, 380, 1920.
*
8
W, Kossel, Ann. d. Physik, vol. xlix, p. 229, 1916; see also G. N. Lewis,
and
J.
Soc.
vol.
Journ. Amer. Chem.
xxxviii, p. 762, 1919,
t
Langmuir, ibid., vol. xli,
2
p. 868, 1919.
182
as singly charged negative ions ; this, according to Kossel, is due

to the fact that their electron systems lack one electron to make up
the stable inert gas configurations and that they endeavour, with
take up the missing electron. Conversely the
atoms following the inert gases, the alkalies (Li, Na, K, Rb, Cs),
loss of energy, to
occur always as singly charged positive ions, and so must easily give
up an electron in their case consequently it may be assumed that
;
an
easily removable electron revolves outside a stable core of the
The positive or negative electro valency of the remainbe accounted for in a similar manner the former is
atoms
may
ing
due to the presence of easily separable electrons, after the removal of
which the inert gas-like core remains the latter is due to the en"
"
electron structures to form
deavour on the part of
incomplete
inert gas type.
complete inert gas configurations by taking up electrons.

The application of this principle to the periodic system leads to
the conception of the shell structure of atoms (see also 29, p. 176).
and He, represents the
The first period, consisting of the elements
structure of the innermost shells.
The system
of
two
electrons of
the inert gas He must therefore be a very stable arrangement.

The second period commences with Li. This element will have a
He atom, external to which a third

the
next element, Be, a further outer
In
bound.
loosely
electron is added, and so on, until at the tenth element, Ne, the
second shell has become a stable inert gas configuration with 8
electrons. This completes the second shell.
The first element of the third period, Na, has again the loosely
bound outer electron, which represents the commencement of the
this closes with the inert gas A, and, since this has the
third shell
core of the character of the
electron
is
atomic number 18, the complete third shell is again made up of

8 electrons.
The process is continued in a similar way, the periods, however,
becoming longer (they contain first 18, afterwards 32 elements).
Among them occur the elements Cu, Ag, Au, which have a certain
resemblance to the alkalies
they
will
thus be characterised by an
easily separable electron and a relatively stable core.

By means of these qualitative considerations, Kossel
was able to
make
a considerable part of inorganic chemistry comprehensible

from the physical standpoint this theory proved particularly fruitful in the domain of the so-called complex combinations, i.e. com;
binations in which ipolecules arise
by the superposition
complexes, which, from the standpoint

theory, are completely saturated.
of
of atomic
the simple valency
183
Langmuir and Lewis have (independently of Kossel) added to

the theory by imagining that the stable configuration of 8 electrons,
which we met with in the case of Ne, A, and the ions of the neighbouring elements, is a cube (octet theory), at the corners of which
these 8 electrons remain in equilibrium. According, then, to these
American investigators, we have to do with static models, a hypothesis
which does not agree with our ideas of atomic mechanics, and which
will therefore not be considered any further here.
The manner in which Bohr arrives at the building up of the atoms
step by step in the order of their atomic number is as follows.
He considers the capture of the most loosely bound electron by
the remainder of the atom. This process takes place by transitions
of this electron between the stationary orbits, regarding which
information is obtained from the arc spectrum of the element.
During this process the atom can be thought of as resolved into a
core and a radiating electron. The core has the same number of
electrons as that of the foregoing atom and a nuclear charge one
unit greater. The first question arising is whether the electrons
in the core have the same arrangement as in the foregoing neutral
atom ? Information is obtained on this point in many cases from
the spark spectrum. The second question is, in what orbit does
the newly captured electron finally move ? It either takes a place
as one of a group of outer electrons already existing in the core, or
it
traverses an orbit not yet occurring in the core. In the former

it adds further to an already existing shell, in the latter case
case
commences a new shell. In order

we must know the quantum numbers
it
to answer these questions
atom.
sometimes
Yes
sometimes
and
question
No in the latter case the same two questions have to be asked
about the last electron but one captured, and so on.
"
The idea underlying this procedure is called by Bohr the Aufbau-
The answer to the
of the orbits in the
is
first
"
prinzip
31.
(atom building).
The Actual Quantum Numbers
of the Optical
Terms
Our next problem will be the more exact determination of the

number of electrons occupying the individual electron orbits and
the values of n and k associated with them. Two methods are availthe examination of the optical spectra and of
able for the solution
:
the X-ray spectra.

If
one goes through the

1
series of
Loc.
cit. t
the elements, and considers in
see p. 181.
184
each case the scheme of the spectral terms, the great similarity
between the spectra of homologous elements will be recognised.
Each alkali spectrum exhibits the same characteristics, likewise each
We
spectrum of the alkaline earths.
numbers
We
in the
attribute this to the equal
of outer electrons
30).
(cf. Kossel,
turn to the term values themselves.
We imagine them written
form
w
vv
*r*
n* 2
of an element can then be expressed by the system

In order to give a survey of the dependence of the
spectrum on the atomic number, we give here the effective quantum
numbers n* of the lowest term of each series, for the arc spectra so
The spectrum
of n*-values.
far analysed, together with the decimal places of the absolute magnitude of the Rydberg correction taken as the limiting value for large
values of n. 1
The
table shows that for neutral
atoms
of almost all elements the
/-terms are still of hydrogen type. The Rydberg corrections are

smallest here for Cu and Ag, apart from the light elements
they
;
are largest for the alkaline earths, and in this case increase in the
order of the atomic numbers. The rf-tcrms arc of hydrogen type
in the case of the lightest elements (i.e. not heavier than
seems probable also that for Cu, Ag, and perhaps for Or,
it
Na)
Mn, the
correction is nearly zero (not approximately equal to another whole
number). The Rydberg correction is still relatively small for the
in the
alkalies, but increases definitely with the atomic number
;
case of the alkaline earths
it is
considerably larger.
p- and s-terms depart considerably from the values
Finally the
in the case of
It appears, consequently, that /-orbits are in general

situated outside the core, that the d-orbits in many neutral atoms
hydrogen.
approach the core too closely to remain hydrogen-like, and in several

actually penetrate into the core,
and that the p- and
The numbers arc mostly calculated from the data
in Paschen-Gotze (Serien-
cases
1
many
In the case of doublets or triplets the mean

gesetze der Linicnspektren, 1922).
value of n* is given ; for the alkaline earths the values in the first and second row
correspond to the singlet and triplet terms respectively, for O, "S they correspond
"
to the triplet and quintet terms, and for He to the singlet and
doublet
(which
are possibly really triplet) terms ; the figures for Cr, Mo refer to septet terms and
those for
to octet terms.
for
of
the
those
alkali
metals
and
He, most
Except
of these spectra, especially those of Cr, Mn, Mo, include terms which cannot be
explained on the assumption of a single radiating electron ; only those terms are
included in the table which can be so explained. From O onwards only the decimal
d are given i the columns for the Rydberg corrections. In those
places of
places where the known terms permit of no extrapolation for n=oo, the Rydberg
correction of the last known is given in brackets.
Mn
The neon spectrum
185
known
to have two systems of terms which converge to

n* the term under consideration has to be counted
which it belongs. The |)-term given is the lowest
which can be assigned to a definite series. A deep-lying term (n*=0-79) is known
from measurements on electron impact (G. Hertz, Zeitschr. f. Physik, vol. xviii,
p. 307, 1923), and from the spectrum in the extreme ultra-violet (G. Hertz, Zeitschr. f.
is
In calculating
different limits.
from the limit of the system to
Physik, vol. xxxii, p. 933, 1925 ; T. Lyman and F. A. Sauniers, Proc. Nat. Acad. Sci.,
vol. xii, p. 192, 1926) ; it corresponds to the normal state, but cannot be explained
on the assumption of a single radiating electron.
186
always penetrating orbits, except in the case of the

very lightest elements. (These conclusions, as far as they are based
on this table, refer to neutral atoms only it is not necessarily true
$-orbits are
that the orbits of the series electron of an ionised atom will be of
the same character as those with the same

the same atomic structure.)
In order to substantiate this view
atomic cores.
The
we
Jc
in a neutral
atom
of
consider the radii of the
sizes of the cores in the case of the arc spectra
of the alkaline earths, or, what comes to the same thing, the sizes
of the singly charged ions of the alkaline earths, can be derived
from the spark spectra. These ions possess only one external
electron
the
the aphelion of its orbit is situated in a region where

the atom has approximately the character of a
field of force of
Coulomb field, and the aphelion distance depends in the same way
on the energy, and consequently on n*, as in the case of hydrogen
:
Since the
first s-orbit is
the normal orbit of the series electron
we take from the spark spectra

n* values corresponding to the first s-terms,
and regard the aphelion distances calculated from them as the core
In the same way we may draw conradii of the alkaline earths.
clusions regarding the cores of the elements Zn and Cd, which are
similar to the alkaline earths, since we must assume also of their
of the ions of the alkaline earths,
of the alkaline earths the
We
obtain
ions that they have only one external electron.
the
alkali
ions
ions
of
Cu
for
the
radii
of
the
and
and
limit
upper
from their distances

salts
an
Ag
of separation in the crystal gratings of their
the separation of the
Na+ and Cl~ ions in the rock-salt grating
must, for example, be larger than the sum of the ionic radii. By
means of such considerations all radii of all monovalent ions are
determined, apart from an additive constant which is additive for
This constant can be
positive and subtractive for negative ions.
determined approximately by putting the two ions K> and Cl~,
both of which are similar to the A-atom, equal to one another
this
K+
must
gives upper limits for the radii of the positive ions, since
be smaller than Cl~ on account of the difference of nuclear charge. 1
second upper limit for the ionic radii of the alkali metals is given
by the known radii of the atoms of the preceding inert gases, deduced
from the kinetic theory of gases
the alkali ions we must regard
;
as being similar in structure to the inert gases

1
Cf.
W.
L. Bragg, Phil. Mag.,
ser. 7, vol.
ii,
their dimensions,
p. 258, 1926.
187
however, must be somewhat smaller on account of the higher nuclear

charge.
The
way are collected in the following

are expressed in terms of the hydrogen radius a 1L as
ionic radii calculated in this
table.
They
unit. 1
The table shows the growth in the core radii of homologous elements with atomic number as well as the fact that the radii of the
alkaline earth cores are relatively large, while those of Cu and Ag
are smaller.
An /-orbit
which
is
has, in a strict
larger
than 8a n
(cf.
Coulomb
24).
a perihelion distance
to the departures from a
field,
Owing
Coulomb
field of force in the neighbourhood of the atomic cores it

be decreased. We shall not carry out this calculation, how2
ever, since for our purpose (the determination of the real quantum
will
numbers) a qualitative consideration suffices. We see that an /-orbit

can most easily approach the core in the case of the heavy alkaline
we understand the large Rydberg correction in the case
earths
;
Ba and
the relatively large ones in the case of Sr and Ca ; we

find generally a complete correspondence between the core radii
of
There are still other methods of determining the radii of the alkali cores, which
The results are in agreement with the upper limits
shall not enter into here.
given here.
Cf. the summary by K. F. Herzfeld, Jahrb. d. Radioakt. u. Ekkj
tronik, vol. xix, p. 259, 1922.
2
The calculations have been carried out by F. Hund, Zeitschr. f. Physik, vol. xxii,
we
p. 405, 1924.
8
The values obtained from
different
Ag salts
are widely different.
188
and the Bydberg
corrections.
This connection enables us to draw
conclusions regarding the ionic radius also in the case of the few
we
other elements the Rydberg corrections of which are known
;
conclude in this
that in the case of

as for
rather smaller for Al than for Mg, and

and Tl it is of the same order of magnitude
that
way
Hg
it is
Zn and Cd.
The d-orbits in the hydrogen atom have a perihelion distance of

more than 4r-5a, (the circular orbit n= 3 has radius 9aH ) in the field
exterior to the cores, which deviates appreciably from a Coulomb
The very small Rydberg corrections in
field, they are smaller.
the case of Cu and Ag we ascribe to the fact that in these cases
the d- or bits are situated at a considerable distance from the core.
The small values for the alkalies and for Zn, Cd, and Hg show that
;
external paths
in the case
close to the boundary of
In the case of the heavier alkaline earths, Ca, Sr, Ba,
in these cases also the d-orbits are

of
Rb and
the core.
still
must approach very
Cs, they
we must assume that penetration
occurs.
In this connection
it is
striking, that in spite of the increase in the core radius from Ca

to Ba, the n* values (for large n) increase ; this leads to the assump-
tion that the
Rydberg
whole numbers and
corrections in the table are to be altered
are, for Ca,
0-95,
1-80 respectively for Ba,

1-75,
the case of Ca the lowest d-teim would
;
by
0-92 respectively
for Sr,
2-77 respectively. In
245,
;
still
correspond to a 3 3 -orbit,
and in the case of Ba to a 53 -orbit. The

cases are worthy of note in which the Rydberg corrections of the
/- and d-orbits do not go hand in hand. Thus in the case of Zn the
in the case of Sr to a 4 3 -,
magnitude of the /-correction is larger, that of the ^-correction

Cd and Hg have considerably smaller d-correcsmaller than for K
tions than Rb and Cs, whereas the /-corrections are about the same.
;
The explanation
ions
of this
is
the high degree of symmetry of the alkali
this causes the potential in the vicinity of their boundaries to
vary in accordance with a high power of r while, in the case of the less
symmetrical cores of Zn, Cd, and Hg, it varies more slowly with r.
In the case of the very light elements, the j?-orbits are still external
}
the smallness of the Rydberg corrections, and small core radii,

suggest that this may also be the case for Cu, Ag, and Au, but the
magnitude of the doublet separations and the variation of the value

of the correction for different atoms of the same atomic structure
++ etc. 1 seem to show
(Cu, Zn+, Ga++, Ge+
)
conclusively that the
,
p-orbits penetrate.
The apparently small Rydberg
corrections for
See J. A. Carroll, Phil. Trans. Roy. Soc., vol. ccxxv, p. 357 (1926).
189
(-0-04 and -0-12), Zn (-0-09 and -0-20), Cd (-0-05 and

Hg (0-00 and 0-10), have certainly to be intheir magnitudes would otherwise be
creased by a whole number
no larger than those of the ^-corrections. If we again note that the
Mg
0-14), as well as
n*-values in the series of the alkalies increase with increasing core

radius, we must assume that the real n-values are 3 for Na, 4 for K,
5 for Rb, 6 for Cs, and that the Rydberg corrections are
0-85,
Their magnitudes for the
3-57 respectively.
1-70,
2-66, and
alkaline earths
must be somewhat
1-12 respectively for Mg;

2-85 respectively for Sr ;
1-04,
2-59,
larger
1-93,
3-73,
we assume,
therefore,
1-95 respectively forCa;

3-67 respectively for Ba.
The
s-orbits penetrate from Li onward. In order that the magnitudes of the Rydberg corrections may increase with increasing atomic
we must take 8 = 1-34 for Na (0-34 would be smaller in

3-13 for Rb, and
2-17 for K
amount than the ^-correction)
4-05 for Cs. The somewhat larger values for the alkaline earths
radius,
may
likewise be found uniquely from the table. For Al we assume

2 to
3
for Ag, Cd
for Cr to Ga values ranging from
5 are very
4 to
3 to
4 for Hg and Tl values between
1-76
from
28, of the Rydberg corprobable. According to the estimate (4),

is
the
factor
the
essential
rection,
principal quantum number of the
largest s-orbit confined to the interior of the core, and this is clearly,
in the case of Cu, Zn, Ga, the same as for Rb, and in the case of Ag,
Cd, In, the same as for Cs

inferred
the values in the sixth period can be
by analogy.
We
supplement this consideration by another rough estimation

of the 8-values for the s-terms, namely, that given by van Urk.
We replace the electron structure of the atomic cores by charged
spherical shells, the radii of which are somewhat larger than â H
must be as large
orbits), and imagine the
(they
as this for the s-orbits to be penetrating

charge of the nuclei (equal to the order
full
in the periodic system) to be operative in thfe interior of the shells.

Since the ^-orbits under consideration have the same angular
190
momentum
as the innermost orbits of the core but smaller
amounts
of energy, and since the field of the core again resembles a Coulomb
one in the vicinity of the nucleus, it follows that the inner loops of
these s-orbits have the same parameter as the core orbits next to
they are therefore subjected to the undiminished

nuclear charge. Application of the equation (2),
28, leads to the
8-values (8 cal ) given in the following table. Together with these the
the nucleus
only S-values (S corr ) which can be in agreement with these lower

and the empirical terms are given.
As a consequence of this we can regard the actual principal
limits
Normal
orbit of last electron added.
See footnote, p. 185.
191
quantum numbers and the actual Kydberg corrections of the empiriwith a few exceptions. To sumcally known terms as determined,
marise these results we now give a table (p. 190) of the negative
8 of the true Kydberg corrections (for large n) and the
of the first terms of each series. The normal state
numbers
quantum
it is distinguished by the fact that the
is denoted by heavy type
lines for which it is the initial state occur in absorption at ordinary
this table only refers
temperatures. It must be emphasised that
to neutral atoms, and it must not be assumed that the relative
of the first term
magnitudes of the terms, or the quantum numbers
ions containing
all
for
in each term series, are necessarily the same
values
the same number of electrons.

32.
The Building Up
of the Periodic System of the
Elements
We
in a position to deal with the building up of the

we have now at
system step by step, for which purpose
are
periodic
now
our disposal all of the data hitherto collected, namely, the properties
of the X-ray spectra ( 29), the chemical behaviour ( 30), and the
characteristics of the optical spectra collected in the table on p. 190
and similar data for many ions.

As a reminder of the order of the elements in the periodic system
we give the scheme (fig. 17) often used by Bohr and dating back to
J. Thomsen.
In the normal state, hydrogen (1 H) has an electron in an orbit
with the principal quantum number 1. As long as the orbit is renumber
garded as an exact Kepler ellipse the subsidiary quantum
the
account
into
on
shall
We
undetermined.
is
taking
see, however,
is also
33, that the total angular momentum
relativity theory in
to be fixed by a quantum condition, without thereby appreciably
altering the energy.

l
The normal
orbit of the electron
is
thus a
r orbit.
the core will correspond,

(2 He) in the excited states
the hydrogen atom in
of
that
with
Bohr's
to
principle,
according
the normal state, the only difference being the higher nuclear charge.
Now the orbit of maximum energy, or normal orbit, of the series
For helium
electron
is
likewise a li-orbit, so that helium in the normal state
would have two (presumably equivalent) ^-electron orbits. This

system will be considered in greater detail later ( 48). According
to Kossel, a special stability must be ascribed to such a system of
two
l r orbits,
such as
is
the case with
all inert
the K-shell.
terminology this structure comprises
gases
in
X-ray
192
The question why there are two systems of terms a singlet system
(parhelium), to which belongs the normal state, and a doublet system
(orthohelium) and why these cannot combine with one another,
cannot be dealt with from the standpoint of our book.
The configuration of two Ij-orbits occurs again in the core of the

excited lithium atom (3 Li). According to the spectroscopic evidence,
the normal state in this case is not a l x - but a 2 r orbit. We must
conclude from this that, according to the principles which limit the
^Hc
Fio. 17.
number
same n k a system of three

under
the
influence
of
a
nuclear
li-orbits
charge 3 is not possible.
The ions Be+, B++, C+++
have a structure similar to that of
the lithium atom. Millikan and Bowen 2 were able to confirm experiof electrons in orbits with the
mentally the fact that the spectra of the

+5 are similar to that of the Li-atom.
"
stripped atoms
"
Be +
to
The spectra
of the two following elements, beryllium (4 Be) and

are
not sufficiently well known for us to be able to draw
(5 B),
conclusions regarding the electronic orbits.
can conclude only,
boron
We
These principles have been formulated by W. Pauli (Zeitschr. f. Physik, vol.

xxxi, p. 765, 1925) but will not be explained in this book.
2
R. A. Millikan and I. S. Bowen, Proc. Nat. Acad. Sci., vol. x, p. 199, 1924
(B++) Nature, vol. exiv, p. 380, 1925 (Be+ and C+++) ; Phys. Pev., vol. xxviii,
1920 (Be+); Phys. Rev., vol. xxvii, p. 144, 1926 (O+ 5 ).
;
p.
256,
193
from the bivalent character of beryllium and trivalent character

of boron, that the newly added electron occupies orbits with the
principal quantum number 2, and that the number of lôrbits
the K-shell is therefore closed with the He
remains equal to two
The spectra of B+ and C++ are known, 1 at least
configuration.
;
in part
they are presumably similar to the spectrum of neutral
Be, and their lowest terms indicate that the normal orbit of the
Also the spark spectrum of carbon
series electron is a 2 1 -orbit.
is
known
2
;
the lowest term occurring in
atom
it is
the 2 2 -term.
Since
most probably similar in structure to the singlecarbon

ion, we may assume that, in addition to the K-shell,
charged
one 2 2- and two 2 1 -orbits exist in boron. We arrive here at the
same result as for lithium, that not more than two equivalent
the boron
is
electrons with Jc=l exist.
further electron
is
added in carbon
(6 C)
and occupies,
in all
probability, a 2 2 -orbit. Such a system of two 2 r and two 2 2-orbits

does not necessarily possess the tetrahedral symmetry with which one
is
familiar
from the chemical and physical properties
(e.g.
diamond
carbon atom. Since, however, nothing is known

the
complicated motions in the atom, this does not necesregarding
a
contradiction.
sarily imply
Too little is known spectroscopically regarding the next elements
(7 N, 8 0, 9 F). The chemical evidence affirms that N, 0, F have
an affinity for three, two, and one electrons, and the spectrum of
shows that the normal orbit of the last electron is a 2 2-orbit. The
eight-shell required by Kossel's theory must be reached in the case
we can assume, therefore, that the
of the inert gas neon (10 Ne)
eight electrons added since Li are bound in orbits with the principal
lattice) of the
quantum number 2. The question as to how they are distributed

3
among the 2 r and 2 2 -orbits we leave unanswered.
The conception of the fully occupied eight-shell is confirmed by
the well-known spectrum of sodium (11 Na). The normal orbit of
the series electron is a 3 1 -orbit, the p-oibit of maximum energy
being a 3 2 -orbit. Outside the core, then, no more orbits occur with
w=2. We conclude from this, that the series of electrons for which
n=2
is
completed by the number 8 reached in the case of neon.
Using the terminology of the X-ray spectra
we
call this structure
R. A. Millikan and I. S. Bowen, Phys. Rev., vol. xxvi, p. 310, 1925.

A. Fowler, Proc. Roy. Soc. (A), vol. cv, p. 299, 1924.
Later investigations by E. C. Stoner (Phil. Mag., voL^xlviii, p. 719, 1924) and
W. Pauli, jr. (loc. cit.), have shown that two of the electrons traverse 2 r orbits and
six 2 a -orbits.
Here and in the following, however, we shall not enter further into
2
these details.
13
194
the L-shell.
The construction
in the second period of the

built up in the first period.
of this L-shell
is
therefore completed
system of elements, while the K-shell
is
magnesium (12 Mg) the normal orbit of the

we assume, in accordance with the
double valency, that the magnesium atom in the normal state has
two equivalent Sj-electrons in addition to the K- and L-shells.
Since in the case of
series electron is again a Sj-orbit,
In aluminium (13 Al), a 3 2 -orbit appears as the normal orbit. We

that a system of three Sôrbits cannot be formed as
see, therefore,
the outside
shell.
In the case of Li and
O we arrived at a
similar
conclusion, namely, the impossibility of the existence of three l r or
2 r orbits.
In the case of
silicon (14 Si)
we meet with an
instance in which
the spectrum can no longer be accounted for with the help of one
"
1
We conclude from the tetravalent character
radiating electron."
that the L-ring
is
surrounded by four orbits with n=3.
With regard
to the following elements (15 P, 16 S, 17 Cl) the only

relevant evidence at present available is the affinities for one, two,
and three
electrons and the spectrum of S which indicates that the

normal orbit of the last bound electron is a 3 2-orbit. The final
element of the period is the inert gas argon (18 A), in which, again,
a closed shell of 8 electrons must exist. The detailed construction
of this shell is best considered from the standpoint of the following element potassium (19 K), the core of which must have this
structure.
The potassium spectrum
indicates a 4 r orbit as the
normal orbit
of the radiating electron, and a 4 2 -orbit as the p-oibit with maximum

energy the series of 3 X and 3 2 -orbits is therefore completed on the
;
attainment of the eight-shell of argon. The 3 3 -orbit of potassium is

more loosely bound than the 4 r and even the 4 2-orbits it has, in
fact, a larger effective quantum number (2-85 in comparison with
;
2'23 for the 4 2 - and 1-77 for the 4 1 -orbit). The closed shells in argon
do not therefore contain all orbits with the principal quantum
number 3, but only the 3 r and 3 2-orbits.
In the case of the divalent calcium (20 Ca), chemical and
spectroscopic results both point to a second electron occupying a
^-orbit.
The elements now following
exhibit very complicated spectra, for
1
Experimental determinations by J. C. McLennan and W. W. Shaver, Trans.
Roy. Soc. Canada, vol. xviii, p. 1, 1924, and A. Fowler, Phil. Trans. Roy. Soc.
London (A), vol. ccxxv, p. 1, 1925. Theoretical interpretation by F. Hund, Zeitschr.
f. Physik, vol. xxxiii, p. 345, 1925 ; vol. xxxiv, p. 296, 1925.

whose resolution
195
into series very few data are at present available. 1
Their terms have a very high multiplicity, e.g. the terms of Mn and
further, the elements have each several systems
of terms, so that, for example, an element can have several
p- or rf-
others are octets
terms of the same multiplicity, which do not belong to a series

the normal state is not always, as hitherto, an s- or y-state
d- and
;
/-terms also occur as normal terms, but the spectroscopic character
paramagnetic
coloured ions
incomplete inter-
20
40
30
50
60
80
70
90
mediate shells with

loosely bound
electrons.
Atomic number
FIG. 18.
of these
terms
is
not determined by one electron only.
Here too
for
time we meet ions having electron arrangements different

from those of the neutral atoms with the same number of electrons
the
first
for
some
of these ions the
normal orbit
of the series electron is a
rf-orbit (see p. 200).
The elements from scandium
to nickel also form, chemically,
a special group. With regard to their chemical valency, they do

not form a continuation of the series K, Ca rather they exhibit
;
multiple valencies which vary irregularly though their

1
maximum
For the connection between these spectra and the periodic system, see F. Hund,
ZeitscJir. f.
Physik, kc.
cit.
196
values correspond in general to their position in the general scheme

V 5-, Cr 6-, 7-valent) the minimum
of the periodic system (Ti 4-,

valency may be as low as 2.
At this juncture the well-known curve
18) of atomic volumes, after Lothar Meyer, can be used as an

example of the relations between different elements (atomic weights
(fig.
and
densities in the solid state).

The alkali elements form sharply
maxima on this curve, which, according to our ideas, arises
defined
from the fact that they have one outer electron in an elliptic orbit.
The fact which concerns us here is that the elements Ti to Ni are
all
situated in the neighbourhood of the third
minimum
of the
further
curve, and have only slightly different atomic volumes.
difference between these elements and the preceding ones arises
magnetic behaviour and the colouration of the heteropolar

compounds in which the elements occur as ions.
from
their
According to Ladenburg, these compounds are paramagnetic for

the group Ti to Cu (the latter only in divalent form) and exhibit
characteristic colouration (cf. fig. 18), i.e. electron jumps exist with
such a small energy difference that they absorb visible light. Previous to Bohr's system of quantum numbers Ladenburg attributed
"
"
in the
intermediate shell
this behaviour to the formation of an
group of elements from Sc to Ni. The newly added electrons are not
to take up positions externally but internally, while the two outer
Ca remain.
Bohr has made this conception more
electrons of
in the
group Sc to Ni, the
series of the
We
by assuming that,
and
3 2 -orbits are com3^
precise
shall consider later

pleted by 3.r orbits.
of inner groups can occur for the present it
;
how such
may
a completion
be mentioned that
the interpretation of the complex spectra of Sc to Ni 2 fully confirm

this assumption. The appearance of the last M-term in the X-ray
spectra of
Cu
(cf. fig.
16, p. 179)
shows that 3 3 -orbits are actually
present in the interior of the atoms of the following elements. The

3 3 -orbits in the core do not prevent the existence of excited 3 3 -orbits
on p. 190 shows for Cu, Zn, Ga, Rb.

The elements copper (29 Cu) and zinc (30 Zn) resemble the alkalies
and alkaline earths respectively in some series of their spectra. In
Cu we have to assume an outer electron confined to a 4 r orbit, and in
Zn two such ^-electrons. Corresponding to Al, the radiating electron
in gallium (31 Ga) is situated on a 4 2 -orbit. In the eighth place
after Ni we have the inert gas krypton (36 Kr), so that the group
in the exterior, as the table
R. Ladonburg, Zeitschr.
taken from this paper.
F.
Hund,
loc. cit.
/.
Elektrochem., vol. xxvi, p. 262, 1920.
Fig. 18
is
197
Cu to Kr resembles very closely the second and third periods. We

assume, therefore, that in this group the eight four-quantum electron
orbits (4 X and 4 2-orbits) are added to the complete three-quantum
-
completed in the case of Ni.

fact that in Kr the N-ring (w=4) is closed is shown by the
they prove, in
spectra of rubidium (37 Kb) and strontium (38 Sr)
conjunction with the chemical behaviour of these elements, that, in
the normal state, we have one and two outer electrons respectively
shell
The
in Sôrbits. The following elements, yttrium (39 Y) to palladium

(46 Pd) (like the group Sc to Ni), do not form a simple continuation
of the series, but exhibit multiple and rapidly changing valency.
This suggests that in these elements the 4 3 -orbits, hitherto absent,

appear for the first time ; in the case of silver (47 Ag) we actually
observe a corresponding X-ray term. The occurrence of 43 -orbits

in the core, again, does not prohibit electrons in an excited state
from moving in a 3 3-orbit outside the

and In.
core, as
is
the case in Ag, Od,
The elements silver (47 Ag), cadmium (48 Cd), and indium (49 In)
correspond in their spectra and chemical behaviour to the elements
Cu, Zn, Ga. In their case one 5 2 and two 5 x-orbits are superposed
on the four-quantum
shell (4 t -,
In xenon (54 X) we
4 2 -, 4 3 -orbits).
must, for the time being, regard the 5^ and 5 2 -groups as closed.
The sixth period begins with caesium (55 Cs) and barium (56 Ba)
in analogy with the fifth
the normal orbits of the radiating electrons
;
Lanthanum
(57 La) and the elements immediately

resemble the group
to Pd.
(78
Pt)
preceding platinum
may
assume there the building up of the 5 3-group ; a 5 3-X-ray term oc-
are 6 1-orbits.
curs, in fact,
group
soon after platinum.
of elements
which
all
In this group
is
We
included a further
have very much the same chemical be-
haviour, the rare earths ; we may ascribe them to the formation of

the 44-orbits, which have not occurred hitherto ; a 44-X-ray term
occurs in the case of tantalum (73 Ta). The elements gold (79 Au) to
niton (86 Nt) correspond to the elements

initial formation of the 6 X- and 6 2-orbits.
Ag
to
The
X, and involve the

last period involves
the superposition of 7 1 -orbits.

We would expect that in the seventh period the addition of
5 4-orbits would give a group of elements of very similar chemical
analogous to the rare earths. The heaviest known

elements do not appear to belong to such a group, so the addition of
5 4-orbits must begin later in the seventh period than the addition
properties,
of 44-orbits in the sixth period
this different is
ascribed to the greater eccentricity
probably to be
and consequent
looser binding
198
of the 5 4-orbits of an element of the seventh period, as compared

with the 4 4 -orbits of the corresponding element of the sixth period. 1
we again cast a glance over the periodic system and omit for
moment those groups (framed in fig. 17) having special chemical
and spectroscopic behaviour, we see that, in the first period, two
If
the
Ij-electrons are added and in each following period altogether eight

n t- and w 2-electrons. The iron group (Sc to Ni) introduces ten
further electrons in three-quantum orbits, so that altogether we

obtain 18 three-quantum orbits. The palladium group (Y to Pd)
introduces 10, and the group of the rare earths 14 further four-
quantum
orbits, the
number
of
which
is
thereby raised to 32.
corroboration of this conception of the building up of inner

electron groups is found (according to Bohr and Coster) in the dia-
gram
of the
X-ray terms
(fig.
in the curves for the values of
16, p. 179),
where marked kinks occur
Z concerned
in this process.
For convenience we give a table of the numbers of electrons occupy2

ing the various shells.
In order to be able to derive deductively the construction of the
periodic table, one must be able to deduce theoretically the maximum
number of electrons which can occupy orbits of the same n k This

can now be done consideration of physical 3 and chemical 4 experimental evidence first suggested the rule that the maximum number
of electrons which can occupy equivalent %-orbits in a single atom
is 2(2&
a theoretical explanation of this rule can now be given, 5
1)
but it lies outside the scope of this book.
If these maximum numbers of occupation be regarded simply as
given, then the order of addition of the quantum orbits becomes, to
a certain degree, comprehensible. We must suppose that the addition of a fresh electron to an already existing configuration takes
place in such a way that the electron finally enters that quantum
orbit in which it has the least energy (in which it is most firmly
bound), and that it remains in this orbit during the capture of subsequent electrons. And here it must be borne in mind that an atom
.
and H. C. Urey (Det. Kongel. Danske Vidensk.

13, 192(5) suggest that in the seventh period the group
to the rare earths should begin with the element atomic number 95.
Calculations by Y. ISugiura
tielskab., vol. vii,
No.
analogous
2
The table gives the numbers of occupying electrons only in as far as they are
determined to a fair degree of certainty trom our considerations. Later investigations permit of these numbers being given with a fair degree of probability also
in the case of the remaining elements.
See Jb\ Hund, Zeitschr. f. Physik, loc. cit.
1 E. C.
Stoner, Phil. Mag., vol. xlviii, p. 719, 1924.
*
J. I). Main Smith, Journ. Soc. Chem. Ind., vol. xliii, p. 323, 1924; vol. xliv, p, 944,
1925 H. G. Grimm anS A. Sommerfeid, Zeitschr. f. Phys., vol. xxxvi, p. 36, 1926.
6
This explanation depends on the work of Pauli (loc. cit.) and the concept of the
;
spinning electron.
SYSTEMS WITH ONE RADIATING ELECTION
199
is not
produced from the preceding one by the addition of an electron,
but from its own positive ion this certainly has the same number
of electrons as the preceding atom, but a somewhat higher nuclear
charge. That this nuclear, charge may on occasion be an important
factor in deciding which orbit of the added electron is most firmly
;
bound
is
shown by the following arguments.
We assume that an ion contains a number of fully occupied quantum
orbits, and we inquire now which of those not occupied is the

most strongly bound. We can give an answer to this in two limiting
cases. If the nuclear charge is much greater than the number of
electrons, the field of force in the ion and its surroundings is nearly
a Coulomb field and the energies of the orbits are in the same order
as in the case of hydrogen, only the p-,
n are
slightly less firmly
the order
is,
therefore
l x,
etc., orbits
rf-,
bound than the
2 lf 2 2 3 lf 3 2 3 3 4 X
,
with a given
s-orbits with the
same n
If now we imagine, say, the uranium atom to be produced by a

nucleus of charge 92 collecting 92 electrons in turn, it will first capture
two l r elcctrons, then altogether eight 2 r and 2 2 -electrons, eighteen
3r, 3 2 -, 3 3 -electrons, etc. Since now the number of electrons gradually
becomes comparable with the nuclear charge, the order of capture is

no longer quite certain. The Bohr-Coster diagram of the X-ray terms
shows us, however, that the energies of the orbits,
(fig. 16, p. 179)
at any rate in completed atoms, are in the order 4 1? 4 2 4 3 4 4 5 X
If the number of electrons is only one less than the nuclear charge,
,
is, if we have to do with the addition of the last electron and the
consequent formation of the neutral atom, we can fall back on the
that
rough estimation of the effective quantum number given by (4),

28, as soon as we have to do with orbits of the penetrating type.
For s-orbits we have
n*=n-(n>-l -!+,).
Since the aphelia of the s-orbits of the core determine its magnitude,
follows that n is the real quantum number of the largest s-orbit
it
in the core,
and therefore ww =w
mately
1.
We
shall
then have approxi-
w*=2.
In the case of the p-orbits n
quantum number
so that we get
will be somewhat larger than the

of the p-orbit completely contained in the core,
2 < n* < 3.
These values agree in a certain measure with the empirical values

1
In general, the dimensions of the d-orbits of
31).
(first table of
1
For half integral values
p-texim.
of k
one finds n* = l-5 for
s- terms,
n*==l-6 to 2-6 for
200
neutral atoms are such that they do not penetrate into the core, or
penetrate to such a small extent that the equation (4), 28, does not
seem to be applicable the 3 3-orbit is then the most firmly bound

and its n* will be somewhat less than 3. Only in the case of
Sr and Ba do the d-orbits appear to penetrate more deeply. The
estimate would lead to
;
d-orbit
the empirical value is approximately 2, but is still higher than for

the s-orbits. In either case, then, the first s-term of a neutral atom
(whatever the value of n)
is likely
to be
more firmly bound than the
first rf-orbit.
This estimation affords an explanation of the fact that after the

completion of an n x and n 2 -group, an outer electron of a neutral
atom
will become bound in an (n+l^-orbit, and that, in conse+ the next

or
quence, after the closing of the 3 X and 3 2 -groups in
traverses a 4 r (not a 3 3 -) orbit, or after completion of
electron in
or Rb+, Rb begins a 5 r (not a 4 3 - or 4 4 -)

group. Whilst in the successive capture of electrons by a slightly
ionised atom the 3 2 -orbit is followed by a 4 1 -orbit, for atoms of high
the 4 r and 4 2 -groups in
Kr
atomic number with the same number of electrons, which are highly
ionised, the 3 2 -orbit is succeeded by a 3 3 -orbit. Consequently, if we
ions K, Ca + Sc ++ Ti +++ V< 4)
traverse the series of
potassium-like
sooner or later, arrive at a point where the outermost
confined to a 3 3 -orbit. Actually, in the spectrum of K, the
,
TJ( 73 )
we must,
electron
is
2-85) is less strongly bound than the 4 r orbit (w*=l-77),

difference is much less (n*=2-31 2-14)
in Sc ++ the n*
of the s-term will be still larger than in the case of Ca+ (in accordance
3 3 -orbit (n*
for
Ca + the
with the general behaviour of the penetrating orbits), so that the

more strongly bound than the s-orbit. 1 It has
d-orbit could be
2
4
recently been confirmed by experiment that for Sc++, Ti+++, V+
the lowest rf-term (3 3 -orbit) is lower than the lowest s-term (ij-orbit),
and similarly 3 in the next row of the periodic table the lowest rf-term
for Yt++, Zr+++ is lower than the lowest s-term. It may therefore be
assumed that, in the building up of the Sc-atom from the argon-like
+
configuration of Sc++ a 3 3 -orbit is added and subsequently two 4 X
++++
two 3 3 and then two 4 X
orbits, and in the case of Ti from Ti
,
orbits. 4
1
ISce N. Bohr, Zcibchr. f. Physik, vol. ix, p. ], 1922.

R. E. Gibbs and H. E. White, Proc. Nat. Acad. Sri., vol. xii, p. 598, 192(5.
3
R. A. Millikan and T. S. Bo wen, Phys. Rev., vol. xxviii, p. 923, 1926.
4
This hypothesis is siif)poitcd by the investigations of these spectra and their
theoretical significance (F. Kund, loc. cit.), even though the conception of a single
"
**
radiating electron is no longer adequate.
2
201
In order to represent the numbers of electrons occupying the

quantum orbits with different n, a two-dimensional diagram must be
with all
employed, for in order to include all the elements together
their ions down to the bare nucleus the values of n must be shown as a
function of both the atomic
z.
An
number Z and of the numbers of
illustration of the ideas in question is
provided by
electrons
fig.
19, in
Pt-Group
Fe-Gioup
10
50
60
70
80
90Z
FIG. 19.
which only the group

of completion,
i.e.
the
regions where this

doubly shaded.
33.
represented (by shading) which is in process

quantum orbit of the last electron added. The
is
quantum
The
orbit
is
not uniquely determined are
Relativistic Kepler
Motion
In our investigations of the periodic system we found the nonrelativistic mechanics adequate. The more rigorous treatment of
202
the orbits in the case of hydrogen requires, however, that the relativity theory should be taken into account.
A simple calculation shows in fact that already in the one-quantum

circular orbit of the
hydrogen atom the velocity of the electron attains
a value whose ratio to the velocity of light

purposes. This velocity is
vu
if
for
% we substitute the value
not negligible for
all
ma n
c is
27rwa 1[
23,
(8),
an
we
find for the ratio
(1)
a=^=-^=7-29.10-3.
For observations which attain this order of accuracy, the ordinary

mechanics will therefore no longer suffice. Consequently we must investigate the motion of an electron in a Coulomb field of force arising
from a nucleus of charge Z, taking the relativity theory into consideration in this investigation we follow Sommerfeld. 1
Here also the Hamiltonian function is identical with the total
energy (cf. (11), 5). We have
;
The components
where fiv/c.
of the
momentum
are
by
which, on squaring and adding, gives

/
-
*-
--
"
yi__p2
and
vT=/
Therefore,
(4)
by
(2),
H
1
A. Sommerfeld, Ann.
d.
Phynik, vol.
li,
p. 1, 1916.
(10),
5,

If
we
calculate
from
this the
sum
of the squares of the
203
momenta, we
find:
L (p
(5)
..
+ft +ft -)
This equation differs from the corresponding one in the non-relativKepler motion by the term
istic
Since this term depends on r only, the present problem is likewise separable in polar co-ordinates.
Now, however, we have single degeneration only. Following the
notation introduced in 21 for the central motion, we write
only.
The action
is 27T
integrals
J and Je are the same as
times the angular
before, in particular
momentum. J r takes the same form
(2),
22,
as before
but here A, B, and C have a somewhat different meaning
=2ro
(-W) --c*-=>Vc
We 2 Z
B=
L I-V+
../
W
mc
a 2Z 2
a being given by (1). The evaluation of the integral gives as before

(c/. (5), Appendix II),
VA/
therefore
.
(
v
Y'
^
A aZ
/
204
the equation be solved for
If
W we
--
-\
find
(6)
2
V +
Z2
We have
here the exact expression for the energy. As in the case

of every multiply- periodic central motion, we know that the orbit is
a rosette.
Only the case in which a is very small is of interest to

few terms of the expansion in a are therefore sufficient.
first
be introduced, in accordance with
The
We find
a4
a 2Z 2
If the value (1) be substituted for
us.
a and the Rydberg constant

23,
(2),
we obtain
w=
(7)}
(
Before we enter into a fuller discussion of this equation, we shall

it, this time using the theory of secular
give another deduction of
perturbations.
We take as our starting-point the expression (4) for the Hamiltonian function. In this the second term under the root is of the
order of magnitude
If
2
/J
we expand
in
terms of this we get
we put
H =
'
if
(PS+PS+P.
/
the Hamiltonian function of the non-relativistic Kepler motion,

which we regard as the unperturbed motion, and H! is a perturbation function. In order to find the influence of this perturbation on
the Kepler motion, we have to average H! over the unperturbed
is
If we express the sum of the squares of the momenta

we obtain
Hj with the help of the equation for
motion.
ring in
occur-
This additional term in the energy corresponds to the additional
term
205
in accordance with
is replaced by
in (5), only in this case
our degree of approximation. We have already calculated the mean
values of 1/r and 1/r 2 for the Kepler motion in (19) and (20), 22
,
~~
2__
ab
so that
Remembering that
a
we
get for the relativity contribution to the energy
or, if
we again
introduce a and R,
in
W^
(8)
agreement with
l~~l
(7).
principal quantum number the larger is the

correction
(8), and it is therefore greatest for the lôrbit.
relativity
For the same value of n it is greater the greater the eccentricity of
The smaller the
The frequency
the orbit.
where
is
of rotation of the perihelion will be
8W
dWi
Ut) 2
fl
ufa
cRZ 2 a 2 Z 2
a2 Z 2
/C
ifC
the frequency of revolution of the electron in
its ellipse.
The terms of the spectrum (H, He+, Li++ ) represented by (7) do

not form a singly ordered set, as do the terms obtained by the nonrelativistic calculation,
but a doubly ordered one.
Since the influence of k on the magnitude of the term is small in

comparison with that of n, we can regard the modification brought
about by the relativity correction as a splitting up of the nonThe arrangement of the terms (with considerable
relativistic terms.
magnification of the relativistic
"
fine structure ") is as follows
3 f
Jt-f
FIG. 20.
123 123*
206
In the absence of external disturbances, only those terms combine,

according to the correspondence principle ( 17), for which the sub-
quantum number k
sidiary
differs
by
The
1.
line series
whose
H the Lyman series) consists of single lines

the line series having the limiting term n= 2 (in H the Balmer series)
limiting
term
is
n=l
(in
<
consists of triplets, the lines of the remaining series
more complex character.

As a measure of the relativistic
fine structure
we
show a
take, following
Sommerfeld, that of the limiting term (n=2) of the Balmer

of hydrogen. This has the theoretical value
Ay
The vahie
Zis
= Ea
ir
still
series
2
-
=0-365 cm- 1
16
for the corresponding
term
in the case of a general value
of
e.g.
for
He +
it is
The quantity Av u will be the approximate

terms of the Balmer series are split up, for the
16A^H
amount by which
all
will be very small.

.)
separations of the variable terms (n=3, 4
With regard to the verification of this theory by observation,
measurements on hydrogen and helium have actually disclosed' the
.
expected components. Regarding the magnitude of the effect, however, the experimental results are not in agreement with one another,
for instance, for which theoretically
measurements on H H^
.,
must be 0-365 cm- 1 vary between 0*29 and 0-39. 1 In the
.
rt ,
Ai>IT
case of
He +
the fine structure
may
be observed in the series
Paschen has made measurements with direct currents as well as with

in the latter case many more lines appear,
alternating currents
since, on account of the rapidly changing field strengths, disturbances
;
arise as a result of which the selection rule based on the correspondence principle breaks down. The numbers of components, as well as
the relative magnitudes of the separations, are in agreement with
the theory. 2
Compare the comprehensive report by E. Lau in Physikal. Zeitechr., vol. xxv,

1924 Lau considers the value 0-29 to 0-30 as the most probable. The new
measurements by J. C. McLennan and (I. M. Shrum (Proc. Roy. Soc., vol. cv,
Measurements by G. Hansen
p. 259, 1924) give, however, again 0-33 to 0-37.
1
p. 60,
support the theory.

In the report by Lau, referred to above, matters are represented as if in the
case of He also the measurements by Paschen gave values smaller than those
(Dis8. t Jena, 1924) also
2
Sr STEMS WITH ONE BADIATING ELECTRON

Sommerfeld
207
has used the relativity correction to explain the

X-ray terms and the departures from Mosley's
and (3), 29. The numerical agreement is surprisingly
multiplicity of the
law,
(1), (2),
good throughout the whole periodic system

theory
volume.
are,
the foundations of the
however, too uncertain to justify
The Zeeman
-84.
its
treatment in this
Effect
we now
Hitherto we have considered atoms as isolated systems
of
constant
external
influences
to
the
action
on
investigate
proceed
;
them, commencing with that of a constant external magnetic

the
Zeeman
field,
effect.
We can start out from a very general atomic model with a stationary nucleus and any number of revolving electrons. We assume
that the energy of the undisturbed system (without magnetic
a function of certain action variables J l9 J 2
.
Wo^,
J2
now a homogeneous magnetic
field)
is
.)

with
to
a
invariant
rotation about the
system
respect
direction of the field. The azimuth <f> of an arbitrary point of the
If
of the
field exists,
is
then a cyclic variable, as proved in 6 and

corresponding conjugated momentum p^ is the angular
of the system about the direction of the field.
system
The
is
17,
and the
momentum
principal function
defines angle variables w tw z

the direction of the field.
w^
w^
is
the
mean azimuth about
In the absence of a magnetic field

does not appear in the
J^
Hamiltonian function, the motion is degenerate and w, is constant.
If now we wish to find the influence of the magnetic field on the
energy, we meet with the case, mentioned in 4, where the forces
which act on the various particles of the system depend on the
velocities.
Owing to the magnetic
field
H (supposed for the moment
required by the theory. This is due to the fact that Lau bases his observations
only on the direct current measurements of Paschen, whereas Paschen includes also
the alternating current measurements.
1
A. Sommerfeld, Ann. d. Physik, vol. li, p. 126, 1916. A. Land6 (Zeitschr. f.
Physik, vol. xxv, p. 46, 1924) has shown that even certain optical doublets, in the
case of terms not of the hydrogen type, follow the appropriate relativity formula.
Millikan and Bowen (Phys. Rev., vol. xxiii, p. 1, 1924, and vol. xxv, p. 295, 1925)
have brought forward much empirical evidence in support of this. These effects
are now ascribed in part to a spin of the electron (cf. footnote, p. 152).
THE MECHANICS OF THE A.TOM
208
to depend arbitrarily on x, y, z), an electron of charge

to the so-called Lorentz force l
e is subjected
K=-%H].
c
(1)
4 we have to determine a function
According to
M such that
dM
M__
dt~8x~~dx~
'
The function
has this property

defined
the vector potential of the magnetic
is
field,
by
H --curl A.
We
have
d d
8A,r
c[
\ 'Ox
tiy
tiz
e,.
The Lagrangian function
(8),
to be taken over
all
is
by
(2)
where the sum

calculate the
is
the electrons.
momenta. For one electron they are

dL
e
From
this
we
p^r^WJ'-^
c
d.f
dL
(S)
^_,^-.A
dL
Pz=-zr=*M
dz
The Hamiltonian function becomes, by
+ypv +*PZ)
Z-
(3),
1
See, for example, M. Abraham, Theorie der Ehktrizitat, vol. ii, third edition,
4, p. 20, or H. A. Lorentz, Theory of Electrons, p. 15.
Leipzig, 1914,

It
is,
209
therefore, equal to the total energy in this case also. No additerm occurs in the energy, corresponding to the magnetic field,
tional
since the magnetic forces
perpendicular to v.
in terms of the
We
If in
the force
c
H we
momenta we
[vH]
is
always
express the velocity components
get
restrict ourselves in the following to the case
weak that we can
so
do no work
neglect the squares of A^,
Ay
where the field is

A z We can then
.
write
H=
(5)
so that the Hamiltonian function differs only
from
its
value for no
by the term
field.
examine the effect of a homogeneous magnetic field H

on the motion of the electrons. The vector potential of such a field is
We now
where r is the position vector from an arbitrary origin, which

as the nucleus. In the additional term we have therefore
we take
where p is the resultant angular momentum of the system of elecand PQ, as above, its component in the direction of the field.
Apart from terms proportional to H, p^ is the momentum conjugate
to an absolute azimuth. If we pass over to the angle and action
variables w lt w 2
of the motion in the absence
w^ J t J 2
J^
of a field, (5) takes the form l
trons,
(6)
From
we can deduce
this
at once the influence of the magnetic

i
by
The double
definition,
sign
J^
is
is
due to the fact that p. can be positive or negative, whereas,
only positive.
1/1
210
field
on the motion of the electrons. The angle and action variables of the motion in the absence of a field remain angle and action
variables in the presence of a magnetic field, since the total energy
depends only on the J 's. The angle variable w^ is, however, no

w where
longer constant, but has the frequency
fc
^=v
=l _El
e
27T
2mc'
corresponding to a wave number
while the frequencies of all the remaining angle variables are exin just the same way as with no field
pressed in terms of the J
fc ,
The
acting.
sole effect of the
magnetic
field
H is then to superpose
on the motion occurring in the absence of a field a uniform precession

of the whole system with the frequency vm (the Larmor precession).
The motion of an electron may then be resolved into oscillations
parallel to the field
pendent of the field,
with frequencies (vr)=^ 1 T 1 +^2 T 2+-
inde-
and
into oscillations perpendicular to the field

with the frequencies (vr)+v m and (vr) vm This, on the classical
theory, would give rise to radiation of frequency (TV) polarised parallel
.
and to radiation with the frequencies

about
the direction of the field.
polarised
to the field
We
shall see that the
of a line into three
Since J 1? J 2
quantum theory
(vr)
leads to the
v m circularly
same resolution
components.
are adiabatic invariants
(cf.
16)
they remain con-
stant in a magnetic field slowly generated, so on switching on the

field the only change in the motion of the electrons is the superposition on the already existing motion of a uniform precession of
frequency v^
To the quantum conditions of the unperturbed system
J k =n kh
there
is
now added a new
condition
J,=mA;
(8)
states that the angular momentum of the electron system in the

direction of the magnetic field can have only certain values. For
it
a weak magnetic field we have here an example of spatial quantisa17. If the angular
tion, which we have dealt with generally in
momentum J/27T, where J is one of the quantities J lf J 2
is fixed
.,
.
by the
quantum number j,
momentum and
the angle a between the directions of the angular

the magnetic field is given by
a=
cos
(9)
211
HI
;
The axis of the angular momentum can therefore be orientated

only in 2j+l different directions (m=j, j 1
j) with respect to
the axis of the field.
.
The
additional magnetic energy
is,
by
(6), (7),
and
(8),
Wm =hvm .m;
(10)
each term
will, in
consequence, be split
terms separated by a distance vm
up
into
2j+l
equidistant
According to the correspondence principle, the quantum number
m can change by
where, for the transition m-+m, the light

polarised parallel to the direction of the field and for
transition m^\-*m it is circularly polarised about the direction
radiated
1, 0,
is
the field. A decrease in

corresponds to a Larmor precessiodnl
the positive sense in the classical theory, and therefore to positive
an increase
circularly polarised radiation
radiation.
negative circularly polarised
;
of
corresponds to
The frequency radiated in the transition m-+m is the same as

the frequency V Q radiated in the absence of a magnetic field for the
same variations of the remaining quantum numbers. The frequency
radiated in the transition
One
m-^l^m
is
consequently for longitudinal observation, as in the

a doublet of circularly polarised spectral lines,
finds
classical theory,
situated symmetrically with

The line with
respect to v
.
the greater
frequency corto
the transition
responds
m+I-*m
it
is
^-^
^--^
(
^
>
)
longitudinal (axis of
lieid directed to front
therefore
positively circularly polarised
with respect to the
field, i.e.
transversal
left-handed to an observer
looking in the opposite direction to that of the field.
~"
For transverse observation

FIG. 21.
observed, the
centre line of which is situated at V Q and
triplet
is
is polarised
parallel to
lines of force, the outer lines being separated*from V Q by
vm
polarised in a perpendicular direction
(fig.
21).
the
and
212
This result
It
is
is
the same as in the classical theory of H. A. Lorentz.

such lines of the other elements as
verified experimentally for
are simple (singlets). This simple theory (which is analogous to the

classical theory of Lorentz), does not suffice for the explanation of
the complicated Zeeman effects which occur in the case of multi"
"
anomalous Zeeman effects lies outside
plets. The theory of these
the scope of this book. 1

36.
The Stark
The next example
Effect for the
of the action of
Hydrogen Atom
an external
which we
field
shall
that of the Stark effect for the hydrogen atom, i.e. the
influence of a homogeneous electric field E on the motion in the
consider
is
hydrogen atom (more generally in an atom with only one electron).

We shall treat this problem in considerable detail, in order to illustrate the various methods employed for its solution.
The first method to which we resort is that of the introduction of
separation variables
2
;
afterwards
we
shall calculate the secular
perturbations by two different methods.

be the same in every case.
If
we choose the
result will, of course,
z-axis of a rectangular co-ordinate
direction of the field, the energy function
m
H=-(x
(1)
The
+2/
system as the
becomes
e z 7i
+z 2 )-
+Ez,
E=|B|.
easy to see that the Hamilton- Jacobi differential equation is

separable neither in rectangular nor in polar co-ordinates. It may,
It
is
however, be
made
separable
by introducing parabolic
co-ordinates.
We put
x=grj cos
<f>
y=r?sin<
(2)
The surfaces
=const. and ry=const. are then paraboloids of rotathey intersect the (x, z)-plane in the curves
tion about the z-axis
X*=2*(--Z
Back and A. Land6, Zeemaneffekt und MuUiplettstruktur der Speki of the German series, Struktur der Materie
(Springer).
1
First worked out by P. S. Epstein, Ann. d. Physik, vol. 1, p. 489, 1916
vol. Iviii,
and
d.
K.
Berl
553, 1919;
Schwarzschild, Sitzungsber.
Akad., 1916, p. 548
Cf.
E.
trallinien, vol.
p.
213
in parabolas with their focus at the origin, and having the parais the azimuth about the direction of the field.
meters 2 and rj 2
i.e.
</>
In the new co-ordinates the kinetic energy
is
T=
(3)
which gives for the momenta conjugated to
77,
<f>
(4)
If
we
we
substitute these in
T and add
get
If this
and the resulting equation multiplied by

be equated to
it becomes separable. We have first
:
88
^=^
since
<f>
is
a cyclic co-ordinate, and
J*=#lVfy
Since p^d^
is
never negative,
J^.^.0 always.
where
(6)
\
/2(,)=2mWr H2a a -?
and
(7)
a 1 +a,=2me2Z.
We find further
214
The action
integrals J^
and J^ are consequently
(8)
where
A=2w(-W),
In order that the integrals (8) shall remain real also for zero external
If the field strength is small, the
field, a i and a 2 must be positive.
1)
D
and
arc
small
in comparison with the remainterms involving x
2
be
evaluated
and
the
approximately by comintegrals may
ing ones
find
We
in
Appendix II), if we take the
(cf. (11),
plex integration.
roots in (8) so that the integrals are positive
_
=
*"2m
2(-2mW)
3a
a x and a a are to be eliminated from the three equations (7) and (9)
evaluated. To a first approximation the term proportional
and
to E in (9) can be omitted and, afterwards, the values of a and a 2
calculated to this first approximation, can be substituted in this
correction term. In this way one finds
tt
2J
+J
meti
*
V-2mW
and then,
2ir
87rV(-2mW)
iising (7),
This gives to a first approximation (omitting the term proportional

to E) the energy of the motion in the absence of a field

and,
if
we
substitute this value of
second approximation
215
W in the correction term, to a
T-
'>
To our approximation, then, the energy depends only on two linear

combinations of the action variables, i.e. we have to do with a case
of single degeneration. This would no longer be the case if we calculated higher terms in E in the expression for the energy. In
accordance with our general considerations ( 15) we now introduce,
in place of
J^, J^, J^,
new
action variables, derived from these
by an
1, and so chosen
integral transformation with the determinant
that the energy (11) depends on only two of the new action variables, and the energy (10) of the unperturbed motion (corresponding
to the double degeneration) on only one of the action variables.

write therefore
We
(12)
=J
:
<P
and obtain
The motion has two frequencies
(14)
and
3E
We
If
we
have two quantum conditions
introduce
them into the expression
(13) for the energy,
we have
SEA*
is again the Rydberg constant (see (2),

23). A more
accurate calculation gives higher terms which depend also on a
third quantum number ri.
where
J, has the same meaning as the correspondingly denoted magnitude of the Kepler ellipse in the absence of at field it can assume
and J only. The sum of the positive quantities
values between
;
216
and J^ lies by (12) similarly between and J and their difference

J and +J. The quantum number ne can therefore
J e between
have only the values
.+n. As will be seen from a
n,
(w
1)
Jj
study of the orbits, the values
are also to be excluded.
The parabolic co-ordinates and rj execute librations between the

will consider the character
zero points of /^f) and/2 (ry) in (6).
of the motion first for the case in which J , and consequently C,
We
Here the region in which /i() and/2 (^) are positive

f=0 and 77=0; the zero points
f mm an(l ^min arc different from 0. The third co-ordinate in this
case performs a rotation. The path is confined to the interior of a
ring having the direction of the field as axis of symmetry and the
does not vanish.
does not extend to the positions
Fia. 22.
bounded by the parabolas f =fmln> =

In particular, if J^==Jn =0,
(cf. fig. 22).
and
coincide and the path is a
rj mm
7y max
cross-section
and
7?=^ ax
and likewise
max
min
and
circle.
max
Since
f mm 4 îmu ^ s pboi& does not pass through the nucleus ; it is displaced

in the opposite direction to that of the external field B, as will be seen
by a consideration of the equilibrium between the positive nucleus and
s
the orbit of the electron in the
field, or by calculating the double

lies on the paraboloid
and
orbit
the
1=^,^
J^=0
J,>0,
= max between the circles of intersection with the paraboloids TJ
and ^=i7 max Finally, in the general case, for Jf >0 and J,,>0, it
lies in a three-dimensional ring.
If we disregard the motion of
roots.
If
^^
<f>,
the (,
co-ordinates in general
completely the curvilinear

the
contained
between
quadrilateral
parabolas for the extreme
values of f and 77, since the frequencies associated with
and
are
77)
different
and
their ratio
is
fill
J^
J^
rational only for certain values of E.
Proceeding to the case J^=0,
<f>
remains constant, the motion
217
takes place in a meridional plane parallel to the direction of the field.

The region in which /x (f ) and/a (ry) are positive comprises the values
f =0 and ^=fO, since in this case/^) and /2 (^) remain positive
there (cf. (6)), i.e. the path completely fills the two-dimensional
region bounded by |=fmax and i?=i7 max
therefore indefinitely close to the nucleus.
The case
in
The
which the electron approaches
orbit approaches
infinitely close to the
to be excluded on principle, just as in the case of central

motions (21). This excludes at the same time the case ne
n,
nucleus
is
nh=J and J^=0.
or
would be equal to
J^
J^
state
stationary
represented by the
since in this case
The
the absence of a
2w
quantum number n
in
up, on application of the field, into

energy with the quantum numbers
field splits
1 states of different
n,=-(-l).
We now consider
-(-2)
+(n-l).
the radiation from such an atom.
frequencies and the possible changes
of
The radiated
n and ne depend on the terms
of the Fourier expansion of the electric moment or of the co-ordinates

of the electron. To the action variables J ,
correspond angle
J^
J^,
With the help of these the Fourier expansion

w^.
of the co-ordinates may be written in the form
variables
w^ w^
Since
w^ and are proportional to one another and performs a
uniform rotation about the direction of the field, the values of r^ for
<f>
<f>
the components of the electric moment perpendicular to the field

are
1 only, and for the component in the direction of the field
is 0.
The co-efficients rf and r^ on the other hand, do
not appear to be restricted (see 36).
Passing over now to the angle variables which correspond to the
the value
action variables J, J e , J',
and
we have
to write (by
J and J e appear in the energy

The Fourier series becomes
since only
stant.
7)
(see (13)), w* is con-
where
,
the angle variable for the motion in the Absence of a field and
corresponds to the revolution of the electron in the elliptic orbit,
is
218
be any integer ; re is also unrestricted, since r^ and

This means that w and n e can change by any amount
so.
are
Ty
consistent with their values, and that frequencies corresponding to
all these transitions will be radiated.
may therefore
The
is derived as follows
If r+r e which is equal to
can
an
even
number,
only be zero. Such a Fourier
2^+r^,
r^
term represents consequently a motion in the direction of the field
a light-wave polarised parallel to the field corresponds then to a
= l
transition for which Aw+An e is even. If An+Ane is odd,
r^
the wave corresponding to such a transition is polarised perpen-
polarisation
is
dicularly to the
We
field.
illustrate the
the Balmer lines
Ha
above remarks by considering the resolution of

H^ ... of hydrogen. The terms which combine
to give these lines are split

.
up
in the following
.
way
(the
,.
give the energy change as a multiple of
-202
-6 -3
-12
-20
-1
-0
03
12
MINI
-/<?
-5
fO
f5
2O
FIG. 23.
We obtain from this for the line Ha (n=3->n=2) the lines

01234 56 8
1
ForH,,:
02
6 8101211
Fio. 25.
numbers

For
Hy
219
II
O2 35
78
10 1Z 73 75 7778 20 22
FIG. 26.
The
calculation of the Stark effect
allows us to illustrate
by parabolic co-ordinates
an
by
example some previous considera-
tions regarding the restriction of the

degenerate action variables.
quantum
conditions to non-
E =0
For
the motion of the Stark effect passes over into the

simple Kepler motion. This is separable in polar co-ordinates as
well as in parabolic co-ordinates. From the separation in polar
|
co-ordinates
quantum
22)
we
obtain the action variables J r
Je
J^,
and the
condition
Jf +J0+J^=ni.
J0+J^
times
is
its
now
times the total angular momentum, and

J^ is 2?r
in
the
direction
of
The
motion
the
axis.
component
polar
2?r
remains separable in these co-ordinates if the field

Coulomb field, but is still spherically symmetrical
case, however, a second quantum condition,
is
J*+J*=**,
To make J^ an integral multiple
to be added.
is
;
of h
no longer a
in the latter
would have no
significance, since the direction of the polar axis of the co-ordinate

would
system is altogether arbitrary and the integral value of
J^/h
be destroyed by a rotation of the co-ordinate system. The restriction J

+3^=kh on the other hand, would lead to no impossibility in
9
the case of the simple Kepler motion.

If now we calculate the Kepler motion in parabolic co-ordinates,
in the above calculations. We obtain the
we have only to put
E=0
action variables J^,
Jn and J^ (the last has the same

and the quantum condition
,
significance as
in polar co-ordinates)
The second quantum condition
Jf-JÂ
must now be dropped, since this
combination of the J's no longer appears in the energy. It has a
meaning only if an electric field is present (though this need only be
which we had in the
a weak
one).
electric field,
220
The
stationary motions in a weak electric field are, however,

essentially different from those in a spherically symmetrical field
differing only slightly from a Coulomb field. In the latter (for which
it
the separation variables are polar co-ordinates) the path is plane
;
an
is
with a slow rotation of the perihelion.
ellipse
In the former
it is likewise approximately an
a
ellipse,
complicated motion in space. If
ellipse performs
then, in the limiting case of a pure Coulomb field, k or n e be intro-
(separable in parabolic co-ordinates)
but this
duced as second quantum number, altogether different motions would

be obtained in the two cases. The degenerate action variable has
therefore no significance for the quantisation.
Our considerations lead to yet another result the calculation of

the Stark effect and the quantising of J e can have a meaning only
if the influence of the
relativity theory, or of a departure of the atomic
;
field of force
from a Coulomb
of the electric field.

istic fine
structure
is
small in comparison with that

our
calculation of the relativformer
Further,
valid only if the influence of the electric fields,
which are always present,
is
field, is
small compared with the relativity
perturbation.
36.
The
Intensity of the Lines in the Stark Effect

of
The correspondence
Hydrogen
principle, which,
by
its
nature, allows of only
approximate calculations of intensities, leads to relatively accurate

results when we are concerned with ratios of intensities of the lines
within a fine structure,
e.g. in
the Stark
effect.
3
Following Kramers, we shall deduce in the following the Fourier
expansion for the orbit of an electron which moves round the nucleus
under the action
of
an external
field
E and
compare the
classical
intensity ratios with those observed. In the Fourier coefficients we

shall omit all terms proportional to E, E 2 , etc., since they lead only
to unimportant corrections.
From 35 we obtain for the principal function
1
Kramers has succeeded in dealing with the simultaneous action of the relativity
variation of mass and a homogeneous field for the case in which the corresponding
changes in the energy are of the same order of magnitude (H. A. Kramers, Zeitechr.
/.
Physik, vol.
*
iii,
p. 199, 1920).
In this section we have given the calculations more shortly than previously in
this book.
*
H. A. Kramers, Intensities of Spectral Lines, Copenhagen, 1919.

If
the values of a x and a a be taken from
W from
(10),
35, both of
them
for
(9),
35,
E=0, we find
221
and the value
of
(1)
where
we
for shortness
write
For the angle variables

from (1) the equations
w^,
w^ conjugate to Jf
J^,
J^
we
find
as
V1
rdr,
*J
(3)
V-
jcJ J
17
\/
as
2^=2.
__
2
/cJ J
I
fdr,
and 77 from
Since the calculation of the w'a as functions of
the above formulae would obviously be very laborious, it is advisable
2
and -q 2 which oscillate between
to write the squares of the variables,
,
two
fixed limits
(cf.
35), in the
form
222
(4)
=a 1 +6 1 cos^,
r)*=a 2 +b 2 coa x
just as before ( 22) we found it convenient to introduce the mean

and eccentric anomalies. In order that the new variables if/ and ^
may
increase
This gives
and
for
by
2?r
during one libration of
or
77,
we must put
^, wn w^ we
find
\J
sin
ij+b 2
sin
sn
sn
o^l+^l COS ^
+
+
J 0^2+^2
In these expressions we have chosen the

of integration in such a
way
COS
still
arbitrary constants
that the final result takes the simplest
possible form.
Introducing the abbreviations
we
get
27TW=or 1 sn
^
'
27^=0"!
The
similarity
sin
0+^2 s n X+X+ 77
i
between these equations and (15), 22, shows clearly

#, and the eccentric anomaly.
down without difficulty the Fourier series for
the analogy between

We can now write
iff,
2
the co-ordinates z and x-\-iy. By (2),
35, z=(f
z does not depend on <f>, it is also independent of w
therefore
:
(8)
where
2
rj ).
.
we
Since
write
L>
a'
i
(7)
i)
Now by
223
COS
Again
since,
by
(4)
and
(5),
a2
al
6 2 cos
&! cos
2
2
COS
J,,)+/<:J (C71
we have
(7 2
COS x),
A 00 =
(11)
/f
J-STT^TT
J^
[*J(J f -J,)+*JVi COB
<tydx
For the remaining values
T T
(l+CTj. COS
,
for
</r-(7 2
cos x)]
^+<7 2 COS X )=(icJ(j
which not both the
J^).
T'S are zero,
the constant term /cJ(Jf Jn ) in z can be omitted at once, since by

(9) it will disappear on averaging. In this way we find (T+T =T)
I)
(12)
K 3*(iyr 2 "(
JO JO
4:7T
COS
If in this
\(e
ix
equation cos
^r
xe
--r
rl
<
-r1tK -r<r t mnx
and cos^ be replaced by ^(e^+er^) and
respectively, it will be seen that the integral on the right

be split up into a sum of products, each factor of which is of the
+e~ lx )
may
form
this is the
well-known expression for the Bessel function
Using the relations
J n (/o).
and
1
E. Jahnko and F. Emde, Funktionentafeln (Leipzig, 1909), p. 169; or see, for
example,. G. N. Watson, Theory of Bessel Functions (Cambridge, 1923), p. 20. The
Bessel functions are here indicated by Gothic letters to avoid confusion with the
action integrals.
2
Jahnke-Emde, op. cit. t p. 165, or Watson, op. cit. t p. 17.
224
we
way from
find in this
(13)
\, ^{
Finally
we
(U)
(12)
get for z
^(J^
is to
(The dash on the summation sign signifies that
be excluded from the summation.) For r=0 the expression (13) is
indeterminate. It follows, however, directly from (12), that the
^=^=0
AT r (^+^=0,
corresponding
r^
+ O)
vanish.
x+iy we take from
In order to calculate the Fourier expansion for

35:
(2),
x+iy^fye*.
(15)
We
can conclude at
once from (15) and
(3)
or
(6),
that
depends only on w^ and wn The most convenient

method of procedure is to expand (x+iy)e 2iri wn" w ^ in a Fourier
(x-\-iy)
e~"
2lrtl
series
(x+iy)W>i-
(16)
In order to write the

deduce from (6)
w4t
=Z, Br T^M^+(
left side of (16)
n+ 1
KL
and x we
as a function Ox
\oa 1 +fe 1 cos0ôa 2 +6 2 cosx/
On
putting
we have
cos
dx
cos
g
(a 2
and consequently, substituting

(18)
+6 2 )(a 2 +6 2 cos x
for (x+iy)
from
(15)
and
(4),

From
this
we can deduce
4:77
Jf
.cos - +*
\
Y*
(we
now write
TT-
We
at once the
225
2^
a^
C
0\/
sm
JO
y
cos-4^
can express the quantities cos
^r,
- sin y
a 2 +6 2
2
cos ^, cos -,
2
etc., in
terms of
exponential functions exactly as in equation (12) and so represent

as a sum of products of Bessel functions.
We obtain finally,
BT T
in the
same way as in the case of the magnitudes AT
(20)
BT
(r=l +rf +r)
=-V(J +^
f
r=0 we can calculate B T T directly from (19).

B T T =0 for r=0, with the exception of the values
For
that
(21)
It
is
found
B_ 1>0 =
Finally, as the Fourier series for
x+iy, we find
(22)
Now that we
have calculated the Fourier
coefficients
we can
pro-
ceed to an approximate estimation of the intensities on the basis

of the correspondence principle. We assume that the simple degeneration of the variables J^, J^,
has
now been removed,
either
which
still
by including
existed in (11),
35,
in the energy terms
quadratic in E, or by taking account of relativity.
226
In accordance with the fundamental principles of the quantum

theory we must then write
J^ =nji
J^
=n^
==
nji.
According to the correspondence principle we find the approximate

intensity of a line corresponding to a transition in which n^ changes
by Anf
and n^ by An^, if we examine the intensity of

n^ by An^,
the harmonic r( =An^, rÂn^, r^==An^ in the classical spectrum
represented by (14) or (22). This leaves open the question whether
the classical spectrum shall be taken to correspond with the initial
,
an intermediate one.
orbit, the final orbit, or
In the following we
shall investigate only the relative intensities within a fine struc-
A
Consequently we
ture.
shall introduce the
magnitudes
B
-
--
"
"
relative amplitudes
R, and then compare the simple arithmetic
mean of the relative intensities 2 corresponding to the initial and
as
final orbits
ducing the
with the observed relative intensities.

"
relative amplitudes
final orbits have the
and
initial
"
One result of intro-
that in forming the average the

same weight attached to them as
is
regards the intensity relations. It may be conjectured that this latter

assumption involves a fundamental aspect of the quantum calculation
in the case of the Zeeman effect, for example, it
the
that
relative
intensities in the Zeeman fine structures
implies
shall be independent of the principal quantum number, a result that
of the intensities
must
from analogy with the classical

and
which
has
verified
been
theory
always
empirically.
From (13) and (20) we find for the z components of the relative
certainly be expected to hold
amplitudes (r^=0,
T^+T =T)
)?
(23)
for the
(24)
(z+iy)-components (r^=

The amplitudes
227
of the ^-components correspond to the lines

those of the (+iy)-components to
;
polarised parallel to the field
the lines polarised perpendicular to the
field.
Ha 6562-8 A
The
table gives a comparison between theory and observation for

The transitions, characterised by the quan-
Ha (n =3->n =2) 6562-8 A.

tum numbers
in the initial
are given in the
placement
E=0
first
and
column.
n
(nf, nf, nfThe second column gives the
final states
of the corresponding lines
dis-
from their positions for
3EA
of the smallest displacement
in multiples
r
(in
v
wave
numbers), as calculated by (11), 35. The third column contains the

values of r^ r r^ corresponding to these transitions in the fourth
and fifth columns the quantities R 2 and R,,2 for the initial and final
;
orbits respectively, are given as a measure of the relative intensities.

The sixth column contains the intensities observed by Stark. The
in order to make a comseventh gives the values of (Ra 2 +R/)
constant
factor is introduced,
a
parison with Stark's values possible
and
observed groups
so that the total intensity of the theoretical
;
of lines are the same.
We
see
from the table that the sum
of the calculated intensities
of the parallel components (1*9), differs considerably from the sum

of the intensities of the perpendicular components (5-0), while ob-
servation gives for each sum nearly the same value (3'3 and 3*6).
The figs. 27 to 30 x represent the comparison between theory and
observation in the case of
by
Stark.
An
agreement between theory and

the absence, required by
35, of the case J^=n^=0.
of the previous
calculations
the
from
we
can
conclude,
up,
observation
To sum
Ha and the other hydrogen lines examined
essential point for the
is
After H. A. Kramers,
foe. ctf., figs. 1
to 4.
228
paragraphs, that the correspondence principle, combined with the

of averaging applied here (taking the arithmetic average of
method
I J
"
.
1
Ha
Hn
calculated
observed
FIG. 27.
Mli
it it
HQ
calculated
III
in
observed
tip
FIG. 28.
.lit,
y~,
If
1,11,,
,1
H^
calculated
observed
Fid. 29.
"
.
..II
,,,
//*
.1 1, ii
calculated
A/5
hi
observed
FIG. 30.
the relative
closely to the
intensities of initial
quantum law of
and
final
intensities.
orbits)
Among
approximates
other things, the

fact that these calculations
229
do not give exactly the true quantum
be expected, since, according to the above calculations, the resolved lines should exhibit a polarisation as a whole
a ), the existence of which seems highly im(mentioned above for
intensities is to
probable both for theoretical reasons and on account of the experimental results.
37.
The Secular Motions of the Hydrogen Atom

an Electric Field
in
The method so far employed for the treatment of the Stark effect
depends on the special circumstance, which might almost be considered accidental, that separation co-ordinates exist having a
simple geometrical significance. We shall now show how we may
attain our object, without making use of this peculiarity, by a
systematic application of the theory of secular perturbations. We
shall adopt two different methods of procedure, beginning with one
which investigates the secular motions of those angle and action
variables which occur as degenerate variables in the investigation
of the Kepler motion by polar co-ordinates
the second method,
which is more suited to the geometrical aspects of the perturba;
tion,
has the advantage of being capable of extension to a more
general case (crossed electric and magnetic fields).

write the Hamiltonian function in the form
We
H=H +AH
(i)
I.
Here
H=
(2)
is
the energy of the Kepler motion in the absence of a
field,
and
denotes the perturbation function. (The field strength E may be

considered as the small parameter A.) According to the rules given
in
18, we have to express the mean value over a period of the un-
perturbed motion,
AHêEz
(3)
and the action variables

which we now denote by
in terms of the degenerate angle variables

of the
w 2Q w 3
,
unperturbed motion (see

and JfJfJj*.
the unperturbed motion
22),
and rj are the rectangular coIf in

ordinates of the electron in the plane of the orbit referred to the
230
nucleus as origin and the major axis as the
2=
-axis,
we have
(fig.
31)
cos
since apart from a constant of integration which can be taken

as zero, 27rw 2 is the angular dis-
tance of the perihelion from the

nodal line, measured in the plane
of the orbit ( 21, p. 137)
and
;
averaging over a period of the un-
perturbed motion
z=sn
In
sn
7rw 2 +rj cos
we found
22
values (see (21),
electrical
electron.
(23'),
If
we express
sin i
"
centre of gravity
and
in terms of
mean
22)
they are the co-ordinates
FIG. 31.
moving
for the
of
"
the
of the
J 1 J a J3 we
get
and
(4)
W^-AH^-sin 2^
etil-
The angle variables w 2 and w3 vary

manner and J3 remains an action variable
w 3 varies in a cyclic
of the perturbed motion.
w 2 is consequently the only non-cyclic co-ordinate in the averaged
perturbation function, and we obtain as the only new action variable
It
may be found as a function of W^ 3 1 Jj and J 3 =J 3 from equaOn evaluating the integral, W : and hence W is found as a
(4).
,
tion
function of the action variables.
We
write for brevity
and
we have then

2
=m
231
dx
where
'-lA -;
If
we
calculate
r-
from the
we
last relation
find
dx
=dl~A
dw 2
sin 3 27TW 2
47rC cos
da?
/B
2nw 2Q \x 2
Ay
\/AC.(o;
-AB)
thus our integral becomes
Since the integrand
is
a rational function of x and the root of an
expression quadratic in
method
of
complex
the integral
x,
We
integration.
find
may
be evaluated by the
(c/. (9),
Appendix
II)
thus
UT o
and,
may
if
/
1
O\
1/1^
TO
o
t/
"
be calculated from this
we
TO
tl 1
we
express a in terms of J A
2
This equation becomes equation
find (on putting
by
3EA 2
(10),
(13),
35,
22,
if
we put
J1
=J 1
232
We show subsequently that our present considerations lead to the

same range of values for Je as found previously. Once again we have
the quantum conditions (15),
35, and the energy equation (16),
35.
We now
examine the secular motions caused by the
electric field.
The
perihelion of the orbital ellipse alters its position relatively to

the line of nodes, and the latter itself moves uniformly about the
It follows from (5) that two periods of the perihelion motion occur during one revolution of the line of nodes.
axis of the field.
This motion of the perihelion, together with its accompanying

phenomena, can best be studied by referring to the curve representing
the motion in the (w 2 J 2 )-plane (fig. 32). Its equation is, by (4),
,
sn
(7)
v
for shortness,
we
(j>
write here
3eEa ll (J 1
2
)
o n (Ji) a /A 2 has been substituted for a in (4)).

It is
Q
If
symmetrical with respect to the straight lines w 2 =% or w 2 =f
Q
or J, or J 2 has one of the values J^ or J 3
0, either w 2 is
x
(using
23,
(9),
For
w2
<0,
the values
1
can no longer have
or ^, or
J 2 the values
the curve is confined to

Ji or J 3
the interior of a rectangle bounded
;
When Wj
|
is
sufficiently small,
w2
can only depart from the immediate

or
when J 2 lies close
vicinity of
to
w/
J^
curve
or
lies
J3
close
The
to
representative
the rectangle
mentioned and passes over into the

circumference of the rectangle for
The curve becomes less extended for larger values of
x |,
FIG. 32.
Wi0.
until
w 2Q
of J (sin
can assume only such values as lie in the neighbourhood

27rw 2Q =l) and, finally, only this value itself; the curve
9
The same holds for

contracts in this case to a point (cf. fig. 32).
is
at
w
For
a given value of
the
2 =f
W!>G, only
limiting point
for
w
are
at
situated
those
the
reversal
2
1?
places where
points
.
sin 27TW 2
is
a minimum, or where
is
J^ and J3 and
a maximum,
233
thus
Ji
being constant.
Now
the function
(1-sXl-y),
where
xy
will
be a
maximum
if
const.,
x=y. Thus
w 2Q
reverses
when
or
-JiJ3
mean of J^ and J3
(J 2
(8)
when J 2
The
field
is
the geometric
secular motions of the orbit under the influence of the electric
are thus as follows
while the line of nodes revolves once, the
perihelion of the orbital ellipse performs two oscillations about the

meridian plane perpendicular to the line of nodes. For a transit
through this meridian plane in one direction, the total
J2
mum
momentum
maximum and
consequently the eccentricity is a minifor a transit in the other direction the eccentricity is a
/27r is
maximum.
Since the component J 3
/27r of
the angular
momentum
in the direction of the field remains constant, the inclination of the

orbital plane oscillates with the same frequency as the eccentricity. It has its maximum or minimum value when the perihelion
passes through the equilibrium position, and it assumes both its

maximum and minimum value twice during one revolution of the
line of nodes.
The major
axis remains constant during this oscilla-
tion of orbital plane and perihelion (since J^ remains constant)

the eccentricity varies in such a way that the electrical centre of
;
gravity always remains in the plane
In this plane
it
describes a curve about the direction of the field
since the inclination
and rotation
frequency ratio 2:1, the curve is closed and, in

revolution, the electrical centre of gravity attains
distance from the axis twice
We shall show later
and
have the
the course of one
of the line of nodes
also its
minimum
its
maximum
distance twice.
38) that the electric centre of gravity executes
an harmonic oscillation about the axis of the field.

We still have the two limiting cases of the perihelion motion to
234
If the representative curve in the (w 2 , J 2 )-plane has contracted to a point (the libration centre), then J 2 =0 and J3 =Ji+J
The orbital ellipse has a constant eccenis an integral multiple of h.
consider.
and constant inclination, and is spatially quantised. The

is perpendicular to the line of nodes
axis
major
J), and
(since w 2
the latter revolves uniformly about the direction of the field. To our
tricity,
not a special state of motion singled out by the

since
J 2 is not fixed by a quantum condition. The
quantum theory,
would
for
J
be arrived at only by a closer approxi2
fixing
necessity
mation in calculating the energy.
approximation
it is
WÔ
or J 2 =J(Ji J 3 ), where the

In the other limiting case,
curve in the (J 2 w 2 )-plane coincides with the perimeter of the
rectangle, the motion is rather complicated. The line of nodes
,
In a certain phase of the motion the orbit is

=Ji), whose configuration is determined by J 3 and J x
revolves uniformly.
circle (J 2
This circle changes gradually into an

the line of nodes
the orbital plane
ellipse,
whose perihelion
lies in
is orientated perpendicular to
the field during this process. Certainly in this configuration the
direction of the line of nodes is indeterminate
but if we define it
;
by continuing the uniform motion which it had previously, the

perihelion lags behind the line of nodes until the separation is TT.
At this stage the orbital plane changes its orientation once more
and the orbit gradually becomes a
circle again.
When
it is
circle,
the position of the perihelion is indeterminate. We can deduce,

however, from the representative curve that it lies once again in the
line of nodes when the eccentricity again increases and the path
once more becomes orientated.

of
During one revolution of the line

nodes the orbit twice becomes a circle.
The range of values of J e or ne is found by the following considera-
J 3 =J3 is positive and at the most equal to J x J3 can never

become zero, for otherwise J 2 would execute a libration between
this would give a limiting
Ji, as can be seen from (4)
J! and
case in which the orbital ellipse would have to traverse a straight
line (Pendelbahn, cf.
21 and 35) and, on account of the incommenof
the
surability
periods of revolution in the ellipse and of the
would
libration,
approach indefinitely close to the nucleus. From
tion.
and the
relation
evident from
fig.
3^, since
3 2 =$3 2 dw 2 by
(4'),
equal to the area of the rectangle in the figure,
we
which
is
find for
at
Je
most
235
J 1 <Je <J 1
and
In place of the single quantum state characterised by a single n,

as in the case of the Kepler motion in the absence of a field, we have
the 2n
1 states
38.
already mentioned in
The Motion
35.
a Hydrogen Atom in Crossed

and Magnetic Fields
of
Electric
Bohr has given another and more illuminating method of calculating the secular motions of the hydrogen atom in an electric
1
2
field.
Using a similar method, Lenz and Klein succeeded in deducing the effect of the simultaneous influence of a magnetic field
and of an electric field arbitrarily orientated with respect to it.
We
reproduce the calculation for the case of an electric
and a magnetic
field
H.
field
The unperturbed motion (E=H=0) has
as such constants we first

six independent integration constants
choose the components of the angular momentum vector P and of
the position vector f of the electric centre of gravity of the orbit.
;
Since
P and f
only five
are always perpendicular to one another, this provides

as the sixth we can choose a
independent quantities
;
magnitude which determines the phase of the motion for this

problem, however, it is unimportant. P and f suffer variations under
the influence of the fields E and H, and we commence by writing
down the differential equations for P and f
Both the electric field and the magnetic field exert couples on the
electron orbit, and these determine the time-rate of variation of
the angular momentum P. On multiplying the equation of motion
;
of the electron, viz.
mi =Ze 2 grad -L -eE+
(1)
vectorially
by
we
Jffi]
get the time-rate of variation of the angular
momentum
p =m[rr] =e[Er] + >[Hr
1
N. Bohr, Quantum Theory of Line Spectra (Copenhagen, 1918), p. 72.

The problem was first solved by P. Epstein, Physical. Rev., vol. xxii, p. 202,
1923 ; O. Halpern gave another solution, Zeitschr. /. fhysik, vol. xviii, p. 287,
The method given here was originally given by W. Lenz (Lecture in
1923.
Brunswick, 1924, and in more detailed form, Zeitschr. f. Physik, vol. xxiv, p. 197,
1924), and 0. Klein, ibid., vol. xxii, p. 109, 1924.
2
236
The
secular
component
of this
motion
is
found by taking the mean
value over a period of the undisturbed motion

bution is
the electric contri-
e[Ef].
The magnetic contribution can

introduce the angular
vector relation
likewise be simply expressed, if we

of the well-known
momentum P by means
[r[Hf]]=[H[rr]]+[f[Hr]J
=i[HP]+[rtHr]],
and remember that the time average
of
[r[Hr]]+[r[Hr]J=|[r[Hr]j
is
zero.
We find in this way

2[r[Hr]J
= -[HP]
and
P^[ES]+[HP].
(2)
The first term represents the couple due to the electric field acting
on an electron situated at the centre of gravity of the orbit the
second term corresponds to Larmor's theorem, and signifies an
additional rotation of the vector P about H with the angular velocity
;
e|H[
2mc'
In addition to the three equations included in (2), we will now
In the first place the mean value of the perturbation energy, taken over a period of the undisturbed motion, is
a constant
find three others.
P and
Secondly,
f are perpendicular, so that
Pf=0,
(4)
and, thirdly,
have from
P and
(23'),
22
f are connected
(p.
through the eccentricity.
145)
||=fac
and from
(8),
22
(p. 141),
We

where J
is
237
the non-degenerate action variable of the motion in the

leads to
field. Elimination of
absence of a
(5)
where
From
and
(3), (4),
an equation
(5) it is possible,
for r of the
with the help of
same form as
differentiated with respect to the time
from
(2),
(2).
(2),
If (3), (4),
and the value
of
to derive
and
(5)
be
substituted
we obtain
0=ff+eK2P[Ef]=f(f+eK 2 [PE]).
This implies, however, that the scalar products of the vector
(7)
f+eK'CPEH^CrH]
with E, P, and f vanish. Since in general these three vectors do

not all vanish nor do they all lie in one plane, the vector (7) must
itself be zero. Consequently
f=eK'[EP] +
(8)
Our problem
(2), (8).
This
is
is
solved
when we can
best accomplished
solve the system of equations
by introducing the new vectors
fx=r+KP
m
(9)
f,=i-KP,
instead of the
unknowns P and f. Since f and KP are perpendicular

two vectors (9) have the same magnitude which,
to one another, the
by
^-[Hf].
(5), is
(10)
|f 1
|=|f 2 l-V^+K^"==|a.
Further, in terms of f and

the equations
the variables f x and f 2 are given
by
238
(2)
and
(8)
now become
(12)
Writing for shortness
^cE ^'
(13)
the system of equations becomes
ra=[-w,+wm
f J.
This denotes simply that the vectors f x and f 2 rotate uniformly

about the axes defined by w e
we
m =(H/2mc)+KE and
m
+w
+w
with
the
velocities
KE
respectively
respective angular
(H/2wc)
At each instant the separation of the end
wm +w and wm W
e
momentum
points of the
1.
two vectors
is
proportional (by (11)) to the angular

half their sum gives the radius vector
and
of the motion,
of the electrical centre of gravity.

consider first the case in which only
We
an
electric field
acts.
both rotate with the same velocity about the direction of

the field, but in opposite directions. In the course of a complete
rotation of each of the vectors they come twice into a configuration
in which E is coplanar with them and they both lie on the same side
of E. In this position their difference, and therefore the resultant
angular momentum P, is a minimum, the eccentricity attains its
fi
and
f2
maximum and
the plane of the orbit deviates least from the equaBetween these positions there are two
torial plane of the field.
others where f^ f 2 and

on opposite sides of E.
,
f2
likewise
lie
in a plane, but with f l
and
P is then a maximum and the eccentricity
a minimum, while the plane of the orbit has its greatest inclination
with the equatorial plane. While the magnitude of P goes through
two librations during such a revolution, the direction P completes
only one rotation,
one revolution.
i.e.
the line of nodes of the orbital plane completes
motion of the electrical centre of gravity be alone considered,

be found directly from the equations (2) and (8) (for H=0).
If the
it
may
If (8)
from
be differentiated with respect to the time and

(2),
we
get
if=e2 K*[E[Ef]].
substituted

This expresses the fact that f
is
239
directed perpendicularly to the
and that r is proportional to the distance of

the electric centre of gravity from the axis of the field, [fE]| / |E|.
The electric centre of gravity performs, in other words, an harmonic
oscillation about the axis of the field (cf.
37, p. 233).
direction of the field
If only a magnetic field is acting, f a and r 2 rotate in the same sense

about the axis of the field with the same velocity
the whole system performs a uniform precession (the Larmor

precession) about the axis of the field.
i.e.
When both fields

different axes.
and f 2 occur about

which we had in the
are acting, the rotations of f x
Thus the simple phase
relation,
case of an electric field only, between the rotation of the line of

nodes on the one hand and the orbital eccentricity and inclination
on the
sets in.
other, will be destroyed and a much more complex motion

Special difficulties arise when the two cones described by
the vectors i l and f 2 intersect.
If the rotation frequencies are

and
the
vectors
f 2 will then approach indefinitely
incommensurable,
TI
close to one another, and, therefore, the angular momentum becomes
indefinitely small.
is
If
now
the frequency of rotation in the ellipse
incommensurable with the other two frequencies, the electron
approaches indefinitely close to the nucleus. On the basis of the

fundamental principles we have previously used, we should have to
exclude such motions. We shall see later, however, when fixing the
quantum conditions, that such orbits may be transformed adiabatically into those of the pure Stark or Zeeman effect which we
must
allow.
We
turn
now
to the energy of the perturbed motion and the
fixing of the stationary states.

Under the influence of the
term
where
(15)
If
we
x is
two
added to the energy
fields
and H, an additional
of the unperturbed motion,
(cf. (3))
W
express here r and
2mc
in terms of f x
and
f2
by
>
and, introducing the vectors
and
wm from
(13),
(11),
we
get
240
(16)
If
we
define the frequencies

"
v'
and
v"
by
m
=5-|w.+w
2
_; m
(17)
I/'
V
\n
I
l
the energy can be expressed in the form
Wî/J'+i/'J",
(18)
where
1
2?r
2'
K' fl
2?r
J/==
J"=
'
By
(6)
and
(10)
we can
1;
'
COs(flj
f 2 COS (f 2
'
'
w ~w
)'
write this
=iJ COS (f 1} W e +Wm

JîJcoBft.w.-wJ.
J'
Since
and
i/
i^"
it follows from the form

and J" are the action variables conjugated
in equation (18) are constant,
of this equation that J'

to the angle variables
The periodicity conditions of 15 are all satisfied. The quantities

and J" are therefore to be determined by the quantum conditions
J'
J'-rc'A
J'W'A.
This implies a somewhat modified type of space quantisation, since
by
(19)
n'
cos(fi,
w +ww )=2n
cosfc,
w -wm )=2-.
n"
The quantum numbers

I
n n\
the range
If the
for then
n'
and n" are thus
restricted in this case to
(-5,5).
^ z/
\
magnetic
field
f
H vanishes we have a case of
degeneration,

The
old action variable
of J'
in
3e =3' + J"
is
241
then to be introduced in place
and J" and we get
agreement with the previous results. In a similar way we have,

pure magnetic field,
J m =J' J"
for a
and
If
we have only a weak magnetic
electric field,
field in
addition to a finite
the axes of rotation of the vectors f x and f 2 have almost
opposite directions. Since the cones generated by these vectors

may not coincide in the case of a vanishing magnetic field (for
this would give P=0 in the Stark effect), they do not intersect in
the case of a weak magnetic
field.
If,
however, we allow
to in-
crease adiabatically, the angles of the cones remain constant and,

similar thing
finally, a point is reached where the cones meet.
when we start with a weak electric field and a finite

magnetic field. The axes of rotation have then very nearly the same
direction, and the cones do not intersect. Nevertheless, by an adiabatic increase of E, a point is again reached when the cones meet,
It is possible, therefore, to transform orbits which we have hitherto
takes place
permitted, and which have been confirmed empirically, into orbits

in which the electron approaches indefinitely close to the nucleus.
At present no explanation
of this difficulty can be given.
There
is
possibility that the J's need not be strictly invariant for the adiabatic
changes considered in this connection, since states are continually
traversed where (non-identical) commensurabilities exist between
the frequencies (" accidental degeneration," see
15, p. 89,
and
16,
p. 97).
39.
Problem of Two Centres
The parabolic co-ordinates used in the separation method to

determine the motion of an electron in the hydrogen atom under the
influence of an electric field are a special case of elliptic co-ordinates.
The latter are the appropriate separation variables for the more
general problem of the motion of a particle attracted to two fixed
centres of force
by
forces obeying Coulomb's law.
If
one centre of
force be displaced to an infinite distance, with an appropriate simultaneous increase in the intensity of its field, we get the case of the
at the same time the elliptic co-ordinates become
Stark effect
;
parabolic.
16
242
apart of the fixed points F x and F a is 2c, the

of a point f 77, distant r l and r 2 from the fixed
co-ordinates
elliptic
are
given by the equations
points,
If the distance
It
is
evident from these equations that
>1,
(2)
and, moreover, that the surfaces
with semi-major axis
and
foci
const, are ellipsoids of revolution

Pj and F 2 whilst the surfaces
,
77=const. are hyperboloids of revolution of two sheets with a distance 2crj between their vertices, and the same focal points. To
determine a point uniquely a third co-ordinate is required, e.g. the
azimuth
<f>
about the
line
FjF 2
Taking cylindrical co-ordinates (r, <, z) with F^Fg as z-axis, and

its mid-point as origin, we can write the equations of these surfaces
of revolution
+
,
If
^ _2
~c
l-7f
These give the equations of transformation
We shall show that the " problem of two centres " referred to above
is
The potential energy of an

separable in the co-ordinates
77, <f>.
e attracted by two positively
charge
charged points is
,
electric
u=-^+fn
1
or, in elliptic co-ordinates
w
The
u=
kinetic energy
"o(^
is

and by the
relations
243
(cf. (3))
r=rf
this takes the
(5)
form
T=
This gives for the
momenta conjugate
.
P(
(6)}
^
=mc
-n
to
77,
<,
*t-j^
?n*
If we express T in terms of the co-ordinates and momenta, and add

the potential energy, we obtain the Hamiltonian function
It will be seen at once that our
tion of the variables.
where C
is
problem
The three momenta
may be solved by separaare found to be
an arbitrary constant and
A-C+1=--
We may now
proceed to investigate the possible types of orbit,

out
of
consideration
individual limiting cases, and restricting
leaving
ourselves to the case of a negative W. We shall A*ot give the method
of proof in detail.
244
I.
ORBITS WHICH ARE COPLANAR WITH THE CENTRES. 1
In this case
p(\
therefore
C-|-l=0 and f=l,

roots
the
of
r)
are
expressions
under the square root sign

(radicand)
in
distinguish
cases
the
We
(8).
following
The radicand
positive for f >1
1.
of
p$ is
then
performs
libration
=1 and
tween
be-
a value
max*
(a)
The
orbit lies within the ellipse =~fmax (fig. 33).

The radicand of p has a root in the interval
(b)
of
positive throughout the

whole interval ~1<^<1.
FIG. 34.
FIG. 33.
The radicand
*s
l<rj<l in ad-
The orbit is then

1.
dition to the roots 77
contained within a region bounded by the ellipse
~ max an(l a hyperbola 7?^const. (fig. 34). The
case in which two roots occur in the interval
I<rj<l does not
The radicand
arise.
> 1 and later
for
of
p^ is negative
assumes positive values in the interval (fnun flnox )
then performs a libration in this interval. In this
2.
case, the radicand of p^
the whole interval
must be
1<^<1.
confined between the two ellipses

(fig.
positive throughout
The curve is then

= min and f = fmaac
Fio. 35.
35).
II.
ORBITS WHICH ARE NOT COPLANAR WITH THE CENTRES. 2
The radicand of p^ is at most positive in an interval ( min inax ),

1
the radicand of
is likewise
which does not extend to
p^
=
can
have
two
or
in
and
four
roots
the
1
interval
for
17
negative
zero
is
not
and
a
rotation
about
performs
1<^<1. Finally, p^
the line of centres. In all cases where motions are possible at all, they
are confined to a ring bounded by two hyperboloids of rotation and
,
<
1
For a detailed discussion of these orbits, see C. L. Charlier, Die Mechanik des
Himmels, vol. i, Leipzig, 1902, iii, 1 (p. 122).
*
Detailed discussion by W. Pauli, jr., Ann. d. Physik, vol. Ixviii, p. 177, 1922,
ii,
6, and K. F. Niessen, Zur Quantentheorie des Wasserstoffmolokul-Iona (Diss.,
Utrecht, 1922), section
1.
245
two ellipsoids of rotation, whose axes pass through the centres (figs.
36 and 37). In the case of double roots two of the ellipsoids or
hyperboloids can coincide limitation motions can also occur.
The regions mentioned here will be completely filled if the motion
In the two cases I, 1 (a) and (6), this would
is not strictly periodic.
involve an infinitely close approach of the moving point to the centres
;
of force.
l
and Niessen
have endeavoured to treat the quantum

two
centres, and to apply it to the hydrogen
problem
molecule positive ion, which consists of two nuclei with charges +e
=Z 2 =l) and one electron. To a first approximation, the
(i.e. Z l
motion of the nuclei can be neglected on account of their large mass.
The first step is to calculate the motion of the electrons when the
Pauli
theory of the
of
FIG. 36.
FIG. 37.
nuclei are an arbitrary distance apart

the nuclear separation has
then to be determined so that the nuclei are in stable equilibrium for
;
definite values of the action variables of the electron motion.
It has
been found in this way that a configuration of minimum energy (the
normal state) is uniquely determined by these conditions (it is of
the type in
fig.
36, the figure being
symmetrical for nuclei with equal
Not only can the value of the energy be found
charges).
in this case,
but the small oscillations of the nuclei, which are brought about by
small perturbations, can also be calculated.
It has been found, however, that the numbers obtained in this
way do not agree with experimental determinations of the ionisation
and excitation potentials. On this account we shall refrain from

more fully this model for H 2 + At present the reason for
the failure of the theory is by no means clear. We shall see later that
discussing
the treatment of atomic problems with the help of classical mechanics

1
W.
Pauli,
toe. tit.
K. F. Niessen,
toe. ctt.
,246
leads to false results immediately several electrons arc present in

we have to deal with a problem involving three
;
other words, whenever

or
more
bodies.
The
artificial
reduction of a multiple-body problem
to a one-body problem, on the basis of the small ratio of electron to

nuclear mass, is, perhaps, not permissible.
FOURTH CHAPTER
THEORY OF PERTURBATIONS
The
40.
Significance of the Theory of Perturbations

for the
Mechanics of the
Atom
we
glance back at the atomic models dealt with in the previous

chapter, we see that they are all characterised by the fact that the
IF
motion of only one electron is taken into consideration. The results

tend to show that, in such cases, our method of procedure is legitimate or, in other words, that we are justified in first calculating
the motions in accordance with classical mechanics, and subsequently singling out certain stationary states by means of quantum
The problem now
conditions.
arises of
how
to treat atoms with
several electrons.
At
glance a similar method would appear applicable to this

mechanical many-body problem being first solved, and
the quantum conditions introduced subsequently. It is well known,
first
case, the
however, what
even in the three-body problem of

still more unfavourable, the reason being that whereas the perturbing forces which two
planets exert on one another in the problems of celestial mechanics
astronomy
difficulties arise
and
in the present case things are
are extremely small in comparison with the attraction of the sun for
either of them, the repulsive force between two electrons in an atom
is
of the
same order
of
magnitude as the force of attraction between
each and the nucleus.
Moreover, in astronomical problems it suffices

to calculate the motions in advance for periods of a few hundred
in atomic theory, on the other hand, only those
can be employed whose course can be repremotions
multiply-periodic
sented for all time by one and the same Fourier series. It appears,
or thousand years
then, that all progress in this direction is barred by insurmountable

analytical difficulties, and so it might be concluded that it is impossible from a purely theoretical basis to arrive at an explanation of
the structures of the atoms right up to uranium.
The object
of the investigations of this chapter is to

247
show that this
THE MECHANICS OP THE ATOM
248
It would, indeed, be remarkable if

is not the decisive difficulty.
Nature fortified herself against further advance in knowledge behind
the analytical difficulties of the many-body problem. Atomic
mechanics overcomes the above-mentioned difficulties arising from
the like order of magnitude of
all
the forces acting, by precisely those
which distinguish it from celestial mechanics, namely,

the quantum restrictions on the possible types of motion. We shall
show, by a systematic development of the perturbation theory, that
it is only the simplest
types of orbits which are of importance in the
and
in astronomy these occur only as exceptional
quantum theory,
cases and so receive no attention. These quantum orbits admit of
characteristics
relatively simple analytical description. One might, therefore, proceed in this way to compute the atoms of the periodic system one
after another.
An
attempt has actually been made to subject to the theory of

perturbations the second simplest atom, that of helium, with its one
The result, however, was entirely negathe discrepancies between theory and observation were much
too large to be accounted for by the inaccuracy of the calculations.
nucleus and two electrons.
tive
This indicates that there
is
some
basic error in the principles of our
atomic mechanics.
When we
set forth these
fundamental principles
16)
we
called
this is shown in particular

attention to their provisional nature
the
fact
that
the
introduces
by
magnitudes such as frequentheory
cies of rotation, distances of separation, etc., which, in all probability,
;
by nature incapable of being observed. Again, the phenomena of

dispersion show that the system is not in resonance with an external
are
alternating electric field of the frequency (TV) calculated by classical

mechanics, but of the quantum frequencies v which are associated
with the quantum transitions.
we have come
Finally, in the course of our investiacross several cases where the failure of our
gations
hypothesis has been indubitably established by experiment, e.g.
"
"
the appearance of
half
quantum numbers, the multiplets and
anomalous Zeeman
The presentation of atomic meeffects, etc.

chanics given here must therefore be regarded as only a first step
towards a final theory, which can be approached only by gradually
eliminating all false trails.
In order to set about this thoroughly, it is necessary to follow
through the method suggested, and to examine the consequences
we are led by the application of classical mechanics in conwith

the quantum restrictions. We shall therefore give in
junction
this chapter a detailed account of the theory of perturbations, into which
249
eluding all cases permitted by the quantum theory finally, we shall

demonstrate the failure of this theory in the case of helium.
We are of opinion that this will not be labour spent in vain, but
;
that this broad development of the theory of perturbations will,

together with the negative results, form the foundation for the true
quantum theory
41.
of the interaction of several electrons. 1
Perturbations of a Non-degenerate System
Even the throe-body problem,
to say nothing of those involving
more
bodies, belongs to that class of mechanical problems which have

not been solved by the method of separation of the variables, and,
In all such cases one is compelled to

back on methods which give the motion to successive degrees
of approximation. These methods are applicable if a parameter A
can be introduced into the Hamiltonian function in such a way that
for A=0 it degenerates into the Hamiltonian function H of a problem
soluble by the method of separation, provided also that it may be
indeed, are hardly likely to be.
fall
expanded
in a series
H=H +AH
(1)
+A 2 H 2 +
.,
which converges for a sufficiently large range of values of the coordinates and momenta.
Problems of this kind are dealt with in celestial mechanics, and
the various methods adopted for their solution are referred to under
"
The additional terms
the heading
Theory of Perturbations."
"
AH 1 +A 2H 2 +
"
... are in fact regarded as a

"
unperturbed motion characterised by
It is only the multiply-periodic solutions
"
perturbation
of the
which are
of
importance
quantum theory. The methods which we shall employ for

deduction in what follows are essentially the same as those
for the
their
which Poincare has treated in

Mecanique
celeste.
By
of a principal function
detail in his M&thodes nouvelles de la
a solution
we mean,
as usual, the discovery
S which generates a canonical transformation,

as
Pk=^r>
v<lk
as
"^ST"'
<Mk
as a result of which the original co-ordinates

formed into angle and action variables.
and momenta are trans-
1 The first
applications of the theory of perturbations to atomic mechanics will
be found in the following works : N. Bohr, Quantum Theory of Line Spectra, parts i,
M. Born and E. Brody, Zcitschr. f. Physik,
ii, iii, Copenhagen, 1918 and 1922
vol. vi, p. 140, 1921 ; P. S. Epstein, Zeitschr. f. Physik voJ, viii, pp. 211, 305, 1922 j
;
vol. ix, p. 92, 1922.

2 Three
vols., Paris,
1892-99.
250
Let us suppose that the unperturbed motion is already known and

assume, for the time being, that this motion is non-degenerate. In
other words, we suppose that there exists no integral relation of the
form
(r^)=r 1 V+... +r,iv =0
(2)
between the frequencies v k of the unperturbed motion, either identically in the action variables J fc or for the special values of the
J fc 's which characterise the initial state of motion.
introduce the angle and action variables w k J k of the

undisturbed motion, and consider the Hamiltonian function of the
We now
perturbed motion defined in terms of them. They are still canonical

co-ordinates, but, in general, they are no longer angle and action
variables in fact, it is evident from the canonical equations
;
an
an
depends on time and that w k is no longer a linear function

becomes the Hamiltonian function
For A=0,
of the
on
which
the
J
's
depends only
unperturbed system,
that J
fc
of time.
fc
(J 1
J2
.)
Similarly, the angle and action variables of the perturbed system

become those of the unperturbed system for A=0.
To
find them,
we have
to look for the generator
J) of a
S(w,
canonical transformation
as
<
3>
*%v.
which transforms the variables

such a
way
dS
"'-af?
W J
Q
into fresh variables w, J, in
as to satisfy the following three conditions
(c/.
15)
The
(A)
position co-ordinates of the system are periodic functions
s
w
of the k with the fundamental period 1.
is transformed into a function
depending only on the
(B)
J*'s.
(0)
S*=S^w J
k
k is
periodic in the
w k s with
the period
1.
The rectangular co-ordinates
of the
system are thus periodic funcin other words, a periodiw

will
in
the
be
transformed into another
A -space
city parallelepiped
in the w^-space. Apart from an arbitrary integral linear transformation of the w k s among themselves with the determinant
1, we
tions of the
w kQ '8,
have, therefore,
as well as of the
wk s
THEOBY OF PERTURBATIONS
w k =wk*+ a periodic function of the wk
(4)
From
this
and from
(C)
we conclude that S
's
251
(period
^w
Jk
1).
is
also peri-
odic in the
wk
's
with period
1.
Or conversely, taking S
2w
k*Jfc
to
be periodic in the w kQ 's with the fundamental period 1, equation

(4), and with it the periodicity of S*, follows from the relation
0s
"nsr;
and
further, since
from the beginning we have assumed that the
position co-ordinates are periodic functions of the w k 's, they must

also be periodic functions of the w k '&. The conditions (A) and (C)
are thus satisfied.
The function S which we require

expansion as a power
now supposed
is
to be capable of
form
S=S +AS 1 +A2S 2 +
(5)
is
series in A, of the
.-..
here the generator of the identical transformation and has

7, p. 31) the form
(cf.
therefore
(6)
and Sx, S 2
are periodic in the w
S possessing these properties leads
conditions (A) and (C).
.
We now
fc
's.
Conversely, every function
to variables which satisfy the
substitute the series (5) for
equation for the perturbed
and expand
in the Hamiltonian-Jacobi
motion
W in turn in powers of A
W-W (J)+AW (J)+A W (J)+:
number
of differential equations then result

powers of A.
on equating the co-
efficients of like
First of all
we have
H (JHW
(8)
i.e.
is
found by replacing
turbed motion.
We
J*.
shall refer to
the energy.
We find the equation for the
coefficients of A, viz.
(J),
by J k in the energy
first
of the unper-
as the zero approximation to
approximation by equating the
252
in
which
(J)
H^w
and
J)
mean
the J's are simply replaced by the
that in
J's,
(J) and
remaining unaltered. The two unknown functions

be determined by means of this equation. Since S x
in the
w kQ 's,
the
mean
value of the
sum
H^w J)
,
the form of the function
and S x may
to be periodic
taken over the unit
in (9),
is
cube of the w-space, or over the time variation of the unperturbed

motion, is zero. It follows, then, from (9) that
W (J)=H^T),
(10)
where Hj is likewise to be averaged over the time variation of the

unperturbed motion. Hence we obtain for AV^ the same expression
as in the calculation of the secular perturbations, although in this
case we have started out from the totally different hypothesis that
the unperturbed motion

theorem
is
Here again we have the
not degenerate.
The energy
of the perturbed
motion
is,
to a
first
approximation,
equal to the energy of the unperturbed motion increased by the time

average of the first term of the perturbation function taken over the
unperturbed motion. Apart, then, from the determination of the

unperturbed motion, no new integration is involved in the calculation
of the energy to this degree of approximation.
After calculation of W^J), we have for S x the equation
"
where the sign ~ over H! denotes the difference

from its mean value
of the function
We may conveniently refer

Hj.
It
may
as the
be represented as a Fourier
without a constant term
summation
to
sign).
If
(this
"
"
periodic
component
of
series
being denoted by the accent on the

as a Fourier series
we imagine S x expressed
the unknown coefficients B r (J) may be expressed in terms

known A T (J) with the* help of (11). It is found that
2V)B (J)=A
T
T (J),
of the
THEORY OP PERTURBATIONS
if
we
253
write
Ir^W
(12)
dJ k
so that i>fc( J) can be derived from the frequencies v k
perturbed motion by replacing J

a solution of (11)
fc
by J
fc
In this
J) of the unway we find as

(
In addition to this there can occur an arbitrary function which depends only on the J 's. We are now in a position to calculate the
influence of the perturbation on the motion to a first approximation.
To this degree of approximation we have for the angle variables
fc
of the
motion
from which the w k 's are given as functions of the time. Superposed
on the unperturbed motion are small periodic oscillations, the amplitudes of which are of the order of magnitude A, and are therefore
proportional to the perturbing forces, while the frequencies
^=ô +A
(15)
8R,i
vJk
deviate but slightly from those of the unperturbed motion.

For the J 's we have
fc
,,_.
which implies that the J^'s, which in the unperturbed motion are
constant, are likewise subject to small oscillations with amplitudes
of the order of A. So-called secular perturbations do not occur, i.e.
quantities constant in the unperturbed motion do not undergo
changes of their own order of magnitude, such as occur in the case
of a degenerate unperturbed motion (cf.
18).
The necessity for the hypothesis of the non-degenerate character
of the unperturbed motion is evident from (13), since, if this were
not the case, the expression (13) would be meaningless, owing to
certain of the denominators vanishing. We see further, however,
that, even if such degeneration be absent, the denominators can be
made
arbitrarily small by a suitable choice of the numbers r l

and, moreover, this may happen for an infinite-ciumber of terms
vary from
oo to
+00
if
rf
the
In view of this, the convergence of the
254
We
Fourier series (13) appears questionable.

shall return to this
at the end of the paragraph and meanwhile continue the formal
development of the method of approximation.
By comparison of the coefficients, more differential equations may

be deduced from (7), the second (coefficients of A2 ) and nih (con
efficients of A ) of which we give below
:
gH
gs 2
a*H
+ _,Hi
"a
as, aSt
8S X
ft
2L^
+ yJ.
dw
7^2!
d3 k
,_
Qgv
aH x
All the equations
oo
C?O
QC!
(7O
*.-*
as n _!
have the form
where n is a function, involving only the results of previous stages

of approximation, and so known at the stage to which (19) refers,
and periodic in the w's, and S n and
n are the required functions.
By forming the time average over the unperturbed motion we find,

in exactly the same manner as in the first stage of the process,
(20)
and
where
O n again denotes
the
"
"
periodic
component
of the function
If
now we
255
again express the right-hand side in the form of a
Fourier series
which no constant term appears, integration of
in
Sn =
(22)'
1
AT
(21) gives
e **W).
^2ni(^f
a formal solution of the proposed problem.

illustration of the method of procedure, we shall carry out
the calculation as far as the expression for
2 in terms of the Fourier
This
is
As an
coefficients of the perturbation function.
By
(13)
where the AT 's are the Fourier coefficients of H 19 and the term for
which T 1 =r 2 =
=T/=0 is absent. The equation (17) for 2 we
.
now
rewrite as
V
0^1 +V I
/
^V
2!
'
'
a,.')
'
z is
obtained by averaging
*T
*_
This can be written
or (what comes to the
We
same
thing, the case (TI>)=() being excluded)
now
consider briefly the question of the convergence of

the series so obtained. The point to be decided is whether the small
shall
values of the denominators (TI>) which
must continually recur
in
the higher terms of the series, will prevent the series being convergent, or whether the convergence can be maintained by corl
has shown
respondingly small values of the numerators. Bruns
1
H. Bruns,
Himmda,
vol.
Aatr. Nachr., vol. cix, p. 215,

p. 307, Leipzig, 1907.
ii,
1884
C.
Charlier,
Mechanik dea
256
that this depends entirely on the character of the frequency ratios

Q J>
2
VI
*v. He deduced the following theorem Those values
"
'
of the periods v kQ for which the series are absolutely convergent

and those for which even the individual terms of the series do not
converge to zero,
J
i> fc
lie
s are functions of
Since the
indefinitely close to one another.
the J^'s, it follows that the function S, de-
rived according to the above procedure, is not a continuous funcSince, on the other hand, this continuity must be
in
that the Hamiltonian equations should be satisorder
presumed,
tion of the jys.
fied
on the
basis of (3)
and the equations
Ja=const.,
wk
an
=t+
const.,
dJk
do not necessarily represent the motion to

when they happen to converge.
These results of Bruns have been supplemented by PoincarS's
l
these lead to the following conditions
Apart from
investigations
it is not possible to represent strictly the motion of
cases,
special
it
follows that our series
any required degree of accuracy, even
the perturbed system by means of convergent /-fold Fourier series in

the time and magnitudes J k constant in time, which could serve
for the fixation of the
quantum
For
states.
this reason it
has
hitherto been impossible to carry out the long-sought-for proof of

the stability of the planetary system, i.e. to prove that the distances
of the planets from one another and from the sun remain always
within definite finite limits, even in the course of infinitely long
periods of time.
Although the method of approximation under consideration is not,
in the strict sense of the word, convergent, it has proved very useful
in celestial mechanics.
It
may
in fact be
shown that the
series
2
If they are discontinued at
possess a kind of semi-convergence.
certain points they give a very accurate representation of the motion
of the perturbed system, not indeed for arbitrarily long periods of

time, but still over what are for practical purposes long intervals.
This shows that the absolute stability of atoms cannot be estabWe may, however, ignore
in- this way.
these fundamental difficulties for the time being and carry out the
lished purely theoretically
calculation of the energy, in order to see if our results are in agreeobservation, as is the case in celestial mechanics.
ment with
1
H. PoincarS,
chap. v.
8
H. Poincare,
Method^
nouvelles de la
Joe. cit., vol. ii,
chap.
Mecanique
viii.
celeste, Paris,
1892-99, vol.
i,
257
Application to the Non-harmonic Oscillator
42.
In the case of one degree of freedom the motion may always be

found by a quadrature (cf.
the desired result, however, is
9)
;
often obtained
more simply by adopting the method
tion described in
of
approxima-
41.
Let us take as an example a linear
oscillator
whose motion
is
slightly non-harmonic, a case already treated by a simple method

(12). Here we will consider an oscillator for which the potential
energy contains a small term proportional to the cube of the dis4

placement y, and a term in j which is of the second order of small
The Hamiltonian function has the form (cf. (3), 12)
quantities.
:
H=H,+AH +A H 2 +
2
(1)
.,
where
"I
fry*
Ho=^
2
2m +^K)Y
(2)
( '
The angle and action variables of the unperturbed motion, in this

case that of the harmonic oscillator, are given by the canonical transformation with the generator (cf. (16), 7)
=cD q
Q 2
or
cot
by
/~J~~
q=
*
*
V 77o>m sin
I
If
we express
si
cos 27rt0.
7T
H in terms of W Q and J
H =vJ,
/
H!=a(
(3)
\l
)
TO
we obtain
sin3
\2
H,=6(-i-)sin:
\7ra>m/
We now find W X (J)

(4)
and
as,
from equation
(9),
41
this gives
W^HÔ,
17
258
From
that in this case the deviation from a linear
(4) it follows
restoring force does not give rise to terms in the energy which are
proportional to the deviation. On the other hand, to this approxi-
mation, the motion does contain an additional term, which arises

from S x
In order to find an additional term in the expression for energy,
we must make a second approximation. From equation (17), 41,
we deduce
.
and
The
calculation gives
J2
15
Wl
(6)
(27r) (i/)
The term proportional to a 2

(9),
is
in
J2
m3
agreement with our previous result
12.
we can deduce from (5) the effect on the oscillation of the

from
a linear restoring force. We find that
deviation
Finally,
and
1 2 J \t
\a
(sin
2<Trw
cos 27rt0-f 2 cos
By solving
w, J in
the
first
the result (11) of
equation for
12
is
arrived at
w and
substituting the values of
by a simple
calculation
(3+C
4WW)
"
259
As an example of a more complicated case, we may indicate the

method of calculation applicable to a spatial non-harmonic oscillator
consisting of any number / of coupled linear non-harmonic oscillators. 1
Its
Hamiltonian function
H=H +AH
(9)
is
+A 2H 2 +...,
where
(10)
kjlm
kjl
we make the convention that
here
same product always

The coefficients have,
different suffixes j, k,
in the
signify different numbers of the set 1, 2,

./.
of course, the same symmetrical properties as
.
the products of the q's which they multiply.

We shall assume that the v k 's are incommensurable.
the angle and action variables
w, J
Introducing
of the unperturbed motion,
we
have
and
in TL 19
we have
to substitute
(*
qk=Qk sm <fc
,
Since
x is
rw~
Qfc= /v /
^
5-, 0*=27r?V
V Trco^m
/
).
a polynomial of odd degree in the q k
s 9 it follows
at once
that
W^HÔ.
(11)
2 we have only to find the Fourier coefficients AT of Hj.

In order to obtain x in the form of a Fourier series we make use
To calculate
of the identity
4 sin a sin
]8
sin
y=
sin
(a+j3+y)+sin
+sin (a
M. Born and E. Brody,
a+]8+y)
j8+y)+sin (a+j8
Zeitachr. /. Physik, vol. vi, p. 140, 1921.
y),
260
we
find
(12)
==
sn
sn
If this
be arranged as a Fourier
series
H 1= 2X sin (^)=
(13)
where
AT =I(BT -B_ r
(14)
the following values are found for the coefficients
W*
al l othcr
fo=i
'
8 zcr
).
(Tfc"3, all other T'S zero),
(^^2,
B_=.
Tj-^1, all other r's zero),
(T*=2, Tj=
other T'S zero),
l, all
(T*=T^=T,=!,
(T*=^f=ljT|=
other T'S zero),

1, all other T'S zero),
all
(in all other cases).
The terms with

(k, j,
J)=(l,
2,
3)
combinations of the T'S
like
and
(1,
3,
2)
and
(2,
1,
3),
^=^=^=1
(e.g.
etc.),
for
are already grouped
together here.
From |AT
2
|
=A A_
T
=4(B T
B_ T ) 2
it
follows that
(15)
all
other T'S zero),
(|T*|=S
all other T'S zero),
f
all
,Q
other T'S zero),
(|T t |=|T,|=|T,|=l,
all other T'S zero),
(in all other cases).
By
(23),
41,
\rohave
261
'
aj,
33,
+v?
**w-*i
'
2
are of the first order in the J's, the quantities
quantities Q
are of the third order, and so
The total
2 is quadratic in the J fc 's.
The
fc
may therefore be written
energy
W=2 **J*+i 2 **J J*
(17)
The
vk,Q
may
kj
be calculated from
(16).
method fails even to this degree of approxione of the following commensurabilities occur
It will be seen that the
mation
if
is, if one frequency of the unperturbed system is twice one of

the others, or is equal to the sum of two others.
The formula (17) finds an application in the theory of the thermal
that
expansion of solid bodies

of polyatomic molecules.
43.
and
in the theory of the
band spectra
Perturbations of an Intrinsically Degenerate System
As we have
seen, certain denominators in the terms of the series
if an integral linear relation exists between the

Q
frequencies V of the unperturbed system, and so the method is not
41 will be zero
of
applicable.
We
consider next the case of
"
intrinsic
"
degeneration,
i.e.
we
assume that a relation

between frequencies v of the unperturbed motion is true identically
in the J's. In this case the angle and action variables w kQ J kQ can
be transformed in such a way that they can be separated into nondegenerate w 's and J a 's, and degenerate wp 's and J p 's (v =0)
,
/)
For
literature
Leipzig, 1923
a
W.
on this subject, see M. Born, Atomtheorie des

Encykl d. math. Wiss., v, 25, 29f.
fasten Zustandes,
also
M. Born and E. Huckel, Physikal Zeitschr., vol. xxiv, p.

Heisenberg, Ann. d. Physik, vol. Ixxiv, p. 1, 1924.
1,
1923; M. Born and
262
(a=l, 2 ...
(15,
p=s+l
/).
depends then only on the Ja
's
p. 91).
We
On
might now try
substituting in the Hamilton- Jacobi equation
would again
(7),
41, equation
but in averaging subsequently over the

1 (^, J) would remain dependent on w*.
unperturbed motion,
We cannot therefore apply the method without further considera(9)
result
The deeper physical reason for this is that the variables WQ

J, with which the angle and action variables w J of the perturbed
motion are correlated, are not determined by the unperturbed
tion.
on account of its degenerate character, other degenerate

motion
action variables, connected with the J 's by linear non-integral
p
0>
relations, could be introduced in place of the J p s, by a suitable
choice of co-ordinates.
;
Our
wp
first
problem
will therefore
be to find the proper variables
J p in place of the w p 's, Jp 's, to serve as the limiting values in

an approximation to w p J p For this purpose we make use of the
,
method
of secular perturbations already discussed
(cf.
18).
It
consists in finding a transformation w J ->wJ such that the first

term of the perturbation function, when averaged over the unper-
turbed motion, depends only on the J's. We assume at the start

we shall return later to the case
that Hj is not identically zero
;
where it vanishes identically.

Hamiltonian- Jacobi equation
H^j.o;
(1)
We
have considered
(1) is
soluble
by
action variables
this
We
have now, as before, to solve a
V,J )=W (JO).
problem
separation of the variables,
w kg
7c
in detail in
18.
If
the equation
we obtain new angle and
If the generator of the transformation is
we have
,.=}.;
We now
motion
introduce'
wk Jk
into the Hamiltonian function of the
H=H (J
(2)
)+AH 1 (w
A!
J^+A'H^',
263
j.)+.
Q
41, try to find the generator S(w k , 3 k )
and, as in
S=S +AS 1 +A2 S 2 +.
of a canonical transformation, which transforms the w 's and J 's

into angle and action variables w k 3 k of the perturbed motion.
This again leads to the equations (9), (17), and generally (18) of
fc
fc
41,
instead of
if,
The
w kQ
solution takes a
J we again write w k J
somewhat different form,
fc
fc
since the quantities
dK
-
vanish.
If
we
solve equation (11) of
41
0J,
=H
where H 1
1
Hj is the periodic component of H l5 there remains
an indeterminate additive function Rj which depends on the
jys and also on the wp 's but not on the w a 's. We shall determine
this in the course of the next approximation. Sj now takes the form
in Sj
where
8^
If this
can be found by solving
(3).
be substituted in equation
(17),
41, for the
next approxi-
mation
(
'
y
+ ~2
*dJa 8w
tt
dJ k dJi 8wk
<>
+H =W
2
all
Kj
2 (J)
the terms in
the terms containing Sx can be taken as known
are not yet known, so that (17), 41, takes the form
;
O being a known function.
It should be noticed that the coefficients
of the quadratic terms in the differential equation differ
both J and J, belong to the J a 's.

S 2 of S 2 may be deter2 (J), Iând a part
equation (6),
mined. Indicating mean values over a unit cube of the w a -space
by a single bar as before, and mean values over a unit cube of the
whole w^-space by a double bar, we have
from zero only
From
further
if
fc
264
where O = O O. This equation is of the same type as (3) and

be solved in an analogous manner. Finally we have also
may
( }
(9)
We can now write

(10)
and determine S 2 as a function of w kQ J from (9) R 2 is a function

of w
Jfc, which so far remains undetermined.
p
The process may be continued the next step determines
3 (J),
R^Wp Jfc) and a part S3 of S3 etc. The final result is again a
,
fc
series for the
energy
W=W (J )+AW (J )+A W (J )+'

2
(11)
/c
fc
These considerations provide a justification for our previous
method of determining the secular perturbations ( 18) by regarding

them as first approximations in a method of successive approximations. The higher approximations lead to periodic variations of the
w kQ 's and J 's, whose amplitudes are at most of the order of magnitude of A. Secular motions of w a Q J a do not occur also in addition
to the secular motions of w
J p which we recalculated in the first
p
fc
stage of the process, only periodic variations occur having frequencies

of the same order of magnitude and amplitudes proportional to A.
We
see further that the terms fL 1
the energy an
duce
amount
of the
=H
second order in
effects of the first order in the
The method hitherto discussed
merely contribute to
although they pro-
A,
motion of the system.
fails if
HÔ
identically (in the
wp
0>
's, Jjfc
s),
a case which very frequently occurs.
more rigorous investigation shows that the secular motion of

wp J p and the additional energy 2 follow from the Hamilton-
Jacobi equation,
if
we
substitute in (5) the expression for Sj given
by (3), and average the equation over the unperturbed motion.

The procedure can be continued, the main object being to eliminate
H! altogether from the perturbation function by means of a suitable
canonical substitution. 1
Further special cases can occur,
e.g.
when the
secular
motion de-
See M. Born and
W. Heisenberg, Ann.
d.
1,
1924.
THEOEY OF PERTURBATIONS
termined by
exist
(1) is itself
265
degenerate, inasmuch as commensurabilities
between the quantities
The
-=1.
secular motions of the vari-
'
ables which are still degenerate to a first approximation would then

have to be found from the second approximation.
44.
The method
An Example
of Accidental Degeneration
of approximation described in
when the unperturbed system

exist relations of the
is
41 can also fail
not intrinsically degenerate,
if
there
form
o
2>*v =o
(i)
fc
for the unperturbed
motion with those values
of the
fc
's
which
In such cases we speak of acciby quantum

dental degeneration. The w .'s may then be chosen so that for those
f)
particular values of J*. the frequencies v p vanish (ps+l
and the frequencies i>a (a--l, 2 ... s) are incommensurable. In the
are fixed
conditions.
7
unperturbed motion, however, the J p 's are also to be determined by

quantum conditions, as already mentioned. Accidentally degenerate
degrees of freedom are therefore subject to quantum conditions,
intrinsically degenerate are not.
Accidental degeneration is a rare and remarkable exception in

astronomy the odds against (1) being exactly fulfilled are infinite.
;
A close approach to it is found
in the case of perturbations of some

minor planets (Achilles, Patroclus, Hector, Nestor) which have very
nearly the same period of revolution as Jupiter. In atomic theory,
on the other hand, where the J 's can only have discrete values,
/{;
accidental degeneration is very common.

may illustrate the most important properties of accidentally
We
1
degenerate systems by a simple example.
Consider two similar rotating bodies of moment of inertia A, with
a common axis, their positions being defined by the angles fa and
as they do not interact they rotate uniformly. The

and
action
variables are given by
angle
<f>
2.
As long
M. Born and W. Hcisenborg,
Zcitschr.
f.
Physik, vol. xiv, p. 44, 1923.
266
where p l9 p% are the angular momenta. The energy
If
we
fix
J^ and J 2 by means
are equal
when
J^^ J
of
quantum
conditions, the
always commensurable
quencies of rotation are
is
two
fre-
in particular, they
Let us now suppose the motion to be perturbed by an interaction

between the two rotators, consisting of a couple proportional to
sin (<i
e energy is then
^ 2)
>
H^
(3)
where
(4)
H^l-cos
and A measures the strength of coupling. In this case we can give

a rigorous solution of the problem of the perturbed motion. If we
carry out the canonical transformation
=<
J^ f J, =J,
then
(J0)2_|_/J'0\2
and this expression involves only one co-ordinate w'. w is cyclic,

and consequently J is constant suppose its value is J. Since the
determinant of the transformation (5) of the J 's is not
1, it follows
that J and J' are not action variables of the unperturbed system.
J can therefore only be fixed by quantum conditions in such a way
that, in passing over to the unperturbed system, J+J' is an integral
;
fc
multiple of h. Instead of J'

motion, the action integral
we have,
(7)
where
167T
If
we put
'(I)
Vl -V si
in the case of the perturbed
267
then
J'
(9)
In order to obtain the energy as a function of the action variables,

(9) must be solved for k and the solution substituted in
the equation
the equation
derived from
(8).
For k>I, w'
executes a motion of libration
within the libration limits

T,
and the integral E(&) has to be evaluated over a complete period

between limits sin $=l/k. For k<l, w' Q performs a rotational
motion the limits of the integral are
and 2?r, and K(k) denotes
;
the complete elliptic integral of the second kind.

For the purposes of further calculation we have to distinguish
between two different cases
:
I.
J1 4 J2
J'
frequencies.
+ 0; the unperturbed motion has two unequal
lOTT
is
not zero, and k vanishes with
Q
sufficiently small values of A, the motion of w'
and for E(&) we can make use of the expansion
A.
For
clearly a rotation,
is
(11)
We find then from
(9)
Jf
and from
II.
(10)
1677
Jf=3f, J'=0,
motion are equal.
We
the frequencies of the unperturbed

J2
shall then have
=0, the denomii.e.
nator in equation (8) will be of the same order as A, and for finite
values of Wj, k2 is of the order of magnitude 1. Both libration and
rotation of w' can occur,
For the larger values of
and the expansion 11) is no longer valid.

and therefore a rotation
lf we have k<l,
268
for the smaller values of

fig.
(cf.
38).
diminishes
(w'
The
for
we have i>l, and hence
1 =0
J')-plane contracts to the libration centre w'=0, J'=0, or

x do not occur since, by (7),
negative values of
w'=, J'=0;
J'
libration
x
approach one another as
the curve representing the motion in the
libration limits
would then be imaginary. Disregarding the limitations imposed
FIG. 38.
by quantum
conditions, all these motions are possible, since

set of values.
can
assume a continuous
The quantum theory

and must,
requires, however, that J' should
be an
V\
;
moreover, J' is proportional to
(by (7))
be
therefore,
capable of becoming arbitrarily small for
integral multiple of
small values of
These two conditions are
A.
fulfilled
only by the
value
In the case of a rotation of w' Q this
is not possible, and for a libration

can hold only in the limiting cases w'=0, J'=0, and w'=,
J'=0. Hence in the perturbed motion the two rotating bodies are
exactly in phase. We have only one frequency, but two quantum
it
conditions.
If all
satisfied
is required is that the equations of motions shall be

without the state necessarily being stable, the cases M>'
that
J'-0, and
=,
w'=f J'=0 are also possible.

,
In any neighbourhood of each of the motions defined by w'=J

and f there are, however, motions of rotation and libration for
which w' takes values widely different from J or |-. For w'=%
or f the motion with a definite phase relation is therefore unstable,
in the mechanical sense of the word. In this case the motions w'= J
and f are also energetically unstable, inasmuch as H is then a maximum. We shall also meet with cases, however, where the mechanically stable motion is energetically unstable.
These special motions can be very simply characterised by the fact
269
that they are the only solutions of the equations of motion

'
for
which w' Q
is
du/_8HL
^___ 2H
~dt
~dt
W*
~~^7
constant and hence for which the bodies rotate with
a constant difference of phase.
It
then follows from the conserva-
tion of energy
that since J
is
According to
H(J, J',w')=W,
must likewise be constant
constant, J'
(6) this
consequently
equation has the solutions
w'=0, 1
f,
Putting (6) into the first of equations (13)
it
then follows that
J'=0.
which the selection of a
example
motion
as
a
stationary state, from the mass of
particularly simple
is
due
mechanical
motions,
entirely to the quantum condicomplex
see
shall
tions. We
quite generally that the simple motions with
have
a special significance.
phase relations
This
is
our
45.
of a case in
first
Phase Relations in the Case of Bohr Atoms and

Molecules
As already mentioned, the
accidental degeneration of the una

very exceptional case in astronomy. In
perturbed system
atomic physics, on the other hand, it plays an important role,
for firstly, according to Bohr's ideas, a whole set of equivalent orbits
occur in the higher atoms and again according to the quantum
is
theory the periods of rotation of the Kepler motions with different

principal quantum numbers are always commensurable, since they
vary as the cubes of whole numbers.
After the discussion of the example in the foregoing paragraph,

expect quite generally, in such cases of accidental de-
we should
quantum conditions would enforce exact phase

and
relations,
consequently particularly simple types of motion.
Since the proof of this for any degree of approximation is somewhat
complicated, and since the necessary mathematical method can only
be given later, we shall indicate here a simpler method by means of
which the phase relations can be found to a first approximation only.
In this section we shall therefore neglect all expressions involving
generation, that the
higher power of A than the
first,
even, for example,
A*.
270
If for the
moment we
disregard the presence of intrinsic degenera-
but assume the existence of several accidental degenerations,

we can choose the angle and action variables wk J k (i=l, 2
./)
tions,
system so that the j>a 's

are incommensurable, while vp
of the unperturbed
from zero and
for the particular values
(a=l, 2
(p=s+l
s) differ
./) vanish
which the J 's have in the case of the unassume therefore that an (/ s)-fold accifc
perturbed motion. We
dental degeneration exists.
We may
write (with an alteration of suffixes from those used

the
Hamiltonian function in the form
previously)
H=H (J
(1)
fc
)+AH 2
,J.
and endeavour to represent the energy constant as a

form
W=W
(2)
If,
as before,
(J*)+AW 2(J
we made the assumption
we should obtain
for
which vanish for A

A at A=0.
powers
Now
is
what
is
required.
fc ).
S 2 expressions in which denominators occur

S is no longer an analytic function of
1
has shown that a series in increasing
form
8=S +VAJS 1 +A8 a +
(3)
Here again
(cf.
41)
and
for
Sj,
fc
S 2 are periodic
in the
wk
(2) if
as
's
(period
in the Hamiltonian function (1),
the form
the
0, i.e.
Bohlin
of A/A of the
series of
1).
If
be substituted
vW k
we obtain an expression
of
the equations
(4o)
(J)=W
(J)
u\
(4l)
aS 2
<*)
2.
are satisfied.
1
K. Bohlin, "t)ber eine neue Annaherungsmethode in der Storungstheorie/*
Bihang till K. Svenska Vet. Akad. Handl., vol. xiv, Afd. i, Nr. 5, 1888 ; see also,
for example, H. Poincare, Methodes nouvelles, vol. ii, chap, xix, and C. L. Charlier,
Mechanik des Himmels, voj. ii, p. 446. The application to the quantum theory is
due to L. Nordheim, Zeitschr. f. Physik, vol. xvii, p. 316, 1923 ; vol. xxi, p. 242,
1924.
W
the
found from (4 ). Since Sj

it follows from (4^ that
is
is
271
to be a periodic function of
wkQ 's,
as,
the quantities
remain, however, indeterminate.
over the unperturbed motion (that
from
is,
over the
w aQ9 s
By
averaging
only)
we obtain
(4)
M-*.
(5)
fc
.-,+....
p and a both refer to accidentally degenerate variables.)

a partial differential equation of the Hamilton- Jacobi type.
It does not admit of integration in all cases, and the method fails,
(Suffixes
This
is
motion for arbitrary values

as
in
the example of 44, that
however,
the motions for which the wp 's are constant to zero approximation,
therefore, for the determination of the
of the JVs.
We can show,
and remain constant also to a first approximation, are stationary

motions in the sense of quantum theory.
We shall now demonstrate this for one accidentally degenerate
degree of freedom, the last (/). In this case equation (5) has the
form
This differential equation of the Hamilton- Jacobi type for one degree
freedom can always be solved by the method of quadratures and
of
we
find
*
2!
The constant
is
an
of integration
must
8J/
satisfy the condition that
From this it follows, according to

a
rotation
(fdwf*=l) or a libration (fdwf*=0)
performs
integral multiple of h.
whether
wf
272
or
The integrand
Hence
tion.
^
OWf
is
never negative along the path of integra-
in the case of rotation
It follows,
i.e.
2 is totally independent of w f
with
this
is
known
about
of course, that
approximation, nothing
for all values of
wf
we must have
In the case of libration, J/ must decrease to zero with VX,

but since on the quantum theory J/ must be an integral multiple of
h, it follows that J/=0, i.e. the integral is to be taken over an
t0/.
infinitely short section of the
tracts therefore to a point.
(w f
J/J-plane
w fQ
Since
is
now
motion, the perturbed motion has only/
the libration con-
constant during the

frequencies, and has
therefore no higher degree of periodicity than the unperturbed
motion.
The value which
(w/)
it
wf
must
'
has for the motion must be a double root of

therefore satisfy the equations
W =H
(9)
and
m,
(io)
3w fQ
The
fact that
can only have certain definite values, namely,

signifies a phase relation in the motion of the
wf
the roots of (10),
system.
If the motion determined in this
way is to be
actually the limiting
and only if this is the case will it be stable the

must be negative in the neighbourhood of the root
case of a libration
radicand of
wf
(6)
i.e.
2!
must have a minimum.

equations of
will still
be
0J/
If the latter condition is
not
fulfilled
the
motion
satisfied,
but in any immediate neighbourhood of the
solution with constant values of w fQ and Jr there will
273
be solutions
of the equations of motion for which the co-ordinates differ widely

from these constant values. The motions determined by (9) and
(10) are thus mechanically unstable.
In the case where
is
positive (as in the
example of the two
dJf
rotators,
of
2.
If,
44), the
mechanically stable motion has the smallest value

is
however,
U<J
negative (this case occurs in atomic
mechanics), the mechanically stable motion has the largest value

and the mechanically unstable the smallest. As yet we
of
2
are unable to decide whether only the mechanically stable motions

are permissible for stationary states. If only the stable motions
are permitted it can so happen that the perturbation energy

2 is a
as opposed to static models where the energy is always
maximum,
a minimum.
If mechanically unstable motions be also allowed

the
(on
quantum theory their neighbouring motions are not allowed
as they do not satisfy quantum conditions) it may happen that the
(state of minimum energy) is included among them.

In order to illustrate this behaviour, consider two electrons revolving in circular Kepler orbits (it is immaterial whether they
revolve about the same nucleus or about different nuclei) and at
normal state
the same time exercising small perturbations on one another. Suppose the position and form of the orbits are fixed, and let us consider
only the variation of the phase of the motion under the influence of
the perturbing forces. The energy of the unperturbed motion is
the unperturbed frequencies are
_ 2A
They are
(J 1 =w 1A; J 2
therefore
_ 2A
commensurable
for
H 2/i), since T 1 ^ 1 -fr 2 v 2 =0
if
each quantum state

r l =n ? r 2
n 23 and
1
these T 1? r 2 are both integral. If now, by means of a canonical substitution, we separate the angle and action variables into those which
are degenerate and those which are not,
_
*"l
_1rtV'!""!
''&""&!*
we have
to put
18
274
we
J2
find
is
the degenerate action variable.
If
we now evaluate
be seen that this expression is negative for all values of J.

Hence in this case the minimum of the perturbation energy
2
corresponds to the unstable motion.
it will
It will be seen that this result
where
is
due to the
fact that
denotes the energy of the unperturbed Kepler motion. It

be true generally when electronic orbits in atoms or
will therefore
molecules exert a mutual influence on one another.

Our considerations show that in the case of one degree of freedom
the motions for which phase relations hold are the only ones possible
according to the quantum theory. The same is true if the equation
(5) is soluble by separation of the variables or can be made so by a
w p 's. Equations of the form (6) are then

obtained for the individual terms of S l3 and all conclusions which
transformation of the
follow from this equation can be arrived at in the same manner.

In the general case, it is true, the necessity for phase relations
it can, however, be shown that there are
cannot be proved
perturbed motions with the same degree of periodicity s as the unperturbed, for which phase relations exist and which are of significance
;
from the point of view of the quantum theory.

The differential equation (5) is equivalent to a system of canonical
equations
in
which
is
the expression obtained by replacing the

"
left-hand side of (5)

"
jugate
momenta
by
"
co-ordinates
"
qp and the
,
wp
's
in the
38
- 's
by the con-
GWp
pp
i.e.
(11)
P*
the quantities v pff
->
being treated as constants. The mechanip
ff
cal
(11) has, in general, several equilibrium

the values of q p =qp Q be determined from
system defined by
configurations
q p =q p
pp =Q
for
if
be solutions of the canonical equations.
will
(12)
H)
is
275
=o
s i= c nst
'
Also
a particular integral of the differential equation

w Q be calculated from the equations
(5), if
the constant
value of
(13)
=0
and
This method
Q
for the
Wp
fails
only if the system of equations (13)

"
"
the
Hessian determinant
is
not soluble
'& 9 i.e. if
3*5,
vanishes.
The motion of the perturbed system found in this way has the
same degree of periodicity s as the unperturbed motion. The fact
that the constants w p Q can have only certain definite values indicates
the existence of phase relations in the perturbed motion.
The motion is stable only if the auxiliary variables q p of equation
The neighbouring motions
(11) have a stable equilibrium for q =q
.
then consist of small oscillations about the particular motion under

consideration.
The
fact that the motions found here satisfy the
tions can be seen as follows.
which
and
it
so,
Jp
is
has in the case of the unperturbed motion
by
Jp
condi-
in addition,
(12),
V-J,
so that
quantum
constant and equal to the value
is
also quantised.
46.
A common
Limiting Degeneration
two cases of Regeneration which

have been considered is the fact that the trajectory occupies a region
characteristic of the
276
than / dimensions
of less
in the co-ordinate space.
third possi-
by the same property, occurs in the case of

it arises in a number of atomic promultiply periodic systems
blems and leads to typical difficulties in the application of the quanbility, characterised
tum
theory.
It
is
somewhat the
therefore advisable to generalise
degeneration and to regard a multiply periodic

conception
motion as degenerate whenever the trajectory occupies a region of
of
dimensions than the number of degrees of freedom.

Generalising our previous terminology ( 15, p. 92), we shall refer
to the number of dimensions of the region of the y-space filled by
the trajectory of the motion as the degree of periodicity of the
less
motion.
motion
is
thus always degenerate
when
its
degree of
is less
than/.
periodicity
We shall consider a system whose motion
may
be found by the
of separation of the variables when unperturbed. As we

have seen ( 14), in separable systems the trajectory in the j-space
is bounded by a series of surfaces, each of the separation co-ordinates
method
backwards and forwards between two surfaces of such a

In certain cases these surfaces may coincide. The number of
dimensions of the region filled by the path is then decreased by 1.
oscillating
series.
This coincidence of two libration limits characterises the third

and,
it
appears, last possibility of a degeneration.
An example will at once make clear what is meant.
Let us take the
Kepler motion, or, in other words, motion in an ellipse with

a perihelion rotation. In general, the path fills a circular ring and,
relativistic
therefore, a two-dimensional region, densely everywhere. The boundaries for the libration of the radius vector are here concentric circles.
If now we suppose the eccentricity of the initial orbit to decrease,
the two limiting circles approach one another until finally they
coalesce and the orbit becomes a one-dimensional circular orbit.
This does not involve any degeneration in the previous sense of the
Actually, however, one angle variable (in this case the longitude of the perihelion) will be indeterminate owing to its geometrical
word.
definition, whilst
one of the action variables assumes a limiting value

For the relativistic Kepler motion, for
consistent with being real.

instance,
we always have J 2 ^ J l9 while here J 2 = J x

"
We may there-
fore call this appropriately

limiting degeneration."
Other examples are provided by an orbit perpendicular to the
direction of the field in the case of the
Zeeman
effect and, in
the case
of the problem of two centres ( 39), by one which is confined to the

surface of an ellipsoid of rotation, etc. For the purpose of illustration we shall continue to speak of circular orbits, eccentricities,
etc.,
although our considerations will have a
277
much more
general
significance.
Let the degree of freedom subject to limiting degeneration be

denoted by the separation co-ordinate qf whose libration limits
,
The action
coincide.
variable corresponding to
has, obviously, the value 0.
If
we
it,
allow perturbing forces to act
on such a motion with J/=0, the degree of freedom qf will in

general be excited (quite apart from the quantum theory) and the
phase integral J f will differ from zero (in our example the path would
not remain circular).
According to the principles of the quantum theory, J f must be an
since it must be equivalent to J/ for a vanishintegral multiple of h
small
ingly
perturbation, it can have only the value zero. We shall
see that the only solution which satisfies this condition is that for
which Jf also remains zero during the perturbed motion. The perturbed motion has therefore (as in the case of accidental degeneration)
the same degree of periodicity as the unperturbed motion.
The problem of finding this solution involves a mathematical
;
difficulty. Eeturning to our example, the perturbation function

contains in general terms which are linear in the eccentricity, that
is
in terms in A/J/. 1
Now
this
can occur quite generally
perturbed system has limiting degeneration.

occur in
dt
i.e.
Terms
in
if
the un-
l/Vjf then
0J/'
in passing over in the limit to the unperturbed motion, the co-
ordinate
wf
have no
finite limiting value.
(perihelion longitude) will vary very rapidly and will

The expansions of 41 are now no
longer applicable.
The behaviour
ordinates
wf
is
3fQw fQ resembles that of polar coindeterminate when J/^0. We can, as a matter
of the variables
difficulty which has been mentioned by re"

"
a
the
Poincar6
them
rectangular canonical co-ordinates
placing
by
of fact,
overcome the
In our previous notation the eccentricity
is
V-S
the degree ot treedom subject to limiting degeneration corresponds to the radial
action integral
Jr=Ji
It is seen at once that, for small
2
Jj.
the eccentricity is proportional to

Cf. H. Poincare, Mithodes nouvelles, vol. ii, chap. xii.
J/-,
VJ
r.
278
(1)
wfQ
Q 2
(the generator of the transformation is %(r) ) tan 27rw f ).
then be varied in the neighbourhood of
without
can
and
J/^0
77
being at the same time subject to rapid variations.

Since in the perturbed motion J/ can deviate but slightly from
the corresponding action variable J/=0, we can consider
and 77
If we substitute the new variables in the Hamiltonian
we can expand this in terms of and 77 in such a way that
to be small.
function,
each coefficient of the powers of A will
and
powers of
77.
On account of (1)
itself
the expansion of
be a series in increasing
and therefore
of the energy
function of the unperturbed motion, proceeds in even powers of

and
since
on
on
it
J
and
not
w
In
the
f
f
77
depends only
only,
perturba.
tion function, on the other hand, linear terms will also occur.
difficulty previously mentioned
The
circular orbit
=0,
77
may now be formulated
=0
is
The
analytically.
indeed an exact solution of the
equations of motion for the unperturbed system, since
d_dH
^77
__
'
~dt~~~~d^
=o,v^-o~~
~di~~drf
but it is no longer so in the case of the perturbed motion, since the

perturbation function contains in general terms which are linear in
's and r7's.
the
This consideration indicates a method of solution.
If,
by a
suit-
can be introduced, such that all

able transformation, variables
77
linear terms in the development of the Hamiltonian function are
,
absent, we have in f =0, 77=0 a rigorous solution of the equations of

motion for the perturbed system as well. This transformation may
be found by means of a recurrence method, the integration of the
remaining equations of motion being accomplished at the same time.
We postulate then a mechanical problem with the Hamiltonian
function
(2)
H=H +AH +AH

1
+...
WV+
WV+
The
H WO
a n bn
,
.'s
(w=l, 2
.)
'
'
'
are here periodic functions of the
waQ 'a
(period
1).
When transformed, the expression (2) must take the
form
H=W +AW +AW,+
(3)
.,
where
(4)
and the
=V n (Ja )+E B
R n 's denote power series in
77
commencing with quadratic
terms.
We assume for the generating function of the transformation
S=2 Ja^+T+^+B^-A7
(5)
7,
where
T=AT 1 +A2 T 2 +.
A.=XA 1 +X*A 2 +
(6)
B=AB +A2 B 2 +...

1
are to be power series in A, whose coefficients
Tn An B n
,
are periodic
functions of the quantities w^

w/-iWe find in this way for the transformation formulae for
.
and
77
(7)
1
?=5
and employing these
The new
order of
in turn
variables difEer therefore from the old only by terms of the

A, so that for AÔ we have once again the unperturbed
circular orbits g Q =r)=Q.

If
now we
carry out the transformation and expand everything
in powers of A, then, to each approximation, there are three, and

n
n which are so far undeonly three, functions available T n
,
A B
,
termined and can be chosen so as to satisfy our conditions.

parison of the coefficients of A in (2) and (3) gives
=V +R
1
Com-
1.
280
On making the coefficients of and 77 zero, equations for AJ and 'B l

are obtained, viz.
Equations of the same type occur very frequently in the theory of

perturbations. To integrate them, A and B are each separated into
a constant part, depending only on the J's, and a purely periodic
component
The former
(10), viz
found from the equations which result on averaging
is
and the latter
is
then found directly from
(10), as in
the case of equa-
As
usual, Vj. and Tj may be calculated as functions

wa 's, from the terms in (9) independent of and rj.
The higher approximations can be obtained in exactly the same
tion (11),
41.
of the J a 's and
way. Since in the case of even the second approximation the formula) are already very involved, we shall not write them down.
Finally, it should be noticed that to the first approximation no new
terms occur in the energy

this is again obtained by
1? but that
w
w
over
in the second approxima10
l
simply averaging
f^ t
a
of
whole
series
new
terms
tion, however,
appears.
The
final result is
an expression
for the
Hamiltonian function in
the form
(12)
H=V(Ja)+c(J a)f +d(Ja)^+e(J )^+
is the Hamiltonian function of a

system in which all co-ordinates
but one are cyclic. The motion may be found in the usual way by
It
solving a Hamilton-Jacobi differential equation for one degree of

and ^ (like
and ^) must vanish with A, we
freedom. Since
need only consider small motions, that

system whose Hamiltonian function is
(13)
is,
those belonging to a
cp+jhf+efr.
By means of a suitable homogeneous linear transformation from f

to new variables X, Y it takes the form
CX +DY 2
2
(14)
v\
If the quadratic
form
"
(13) is
definite,"
sign in (14), the motions in the

f =77=0 are small oscillations of
i.e.
281
C and D have the same
X=Y=0
neighbourhood of
and Y about this point.
or
The
only motion compatible with the quantum condition
one in which
and T? remain zero. The energy of this particular
is a minimum, if the quadratic form is positive definite
it is
a maximum if the form is negative definite.
If the quadratic form (13) is indefinite there are motions in each
is
state
and rj do not remain small.

neighbourhood of f ==^=0, for which
The only values which satisfy the equations of motion and the
quantum condition are again
rj=Q: the motion is, however,
mechanically unstable.
In every case the perturbed motion has the same degree of periodi-
city/!,
whilst
its
energy
is
W=V(Ja
(15)
).
The restriction to simple limiting degeneration

The corresponding considerations and calculations
is
limiting degeneration of arbitrary multiplicity.

expression for the generator S is
The appropriate
not necessary.
are also valid for
S=iX'
(16)
The result
of the transformation
is
an expression
for
H in the form
H=v(ja
(17)
to which must be added terms of the third and higher orders in

The Hamilton-Jacobi equation to which this function leads
T? P
.
,,
is
We
need exnot, in general, separable for finite values of f p 7j p

amine, however, only those motions for which g p and t] p remain
small. By means of a suitable homogeneous linear transformation,
,
the quadratic terms in (17)
may
be written in the form
H=V(J.)+2(C,X,+D,Y,).
(18)
now
separable. The only motions compatible with the

are those for which X Y and
conditions
quantum
consequently
p
p
is
are always zero.

p rj p
The conditions for stability are analogous to those in the case of
,
one degree of freedom. The particular motion ^p =^ p =0 is stable

when, and only when, the quadratic form i (17) is definite. The
energy is a minimum if it is positive definite.
282
To summarise, we may
state
For an initial motion possessing
the
limiting degeneration,
perturbed motion, selected in accordance
with the quantum theory, has the same degree of periodicity 8 as
the unperturbed motion.
Its energy
is
W=V(JJ.
(19)
47.
Phase Relations to any Degree of Approximation
45 we had to leave unanswered the question whether, in the

case of an accidentally degenerate initial motion, the motions singled
out by the quantum theory have the same degree of periodicity as
In
when the work is carried to any degree of approximaThe method developed for limiting degeneration now enables
us to answer this question. At the same time the restriction on the
the
initial one,
tion.
wpQ 's given
in
45 will be established by an independent method.
Let us again state the problem we wish to study those motions
of the mechanical system with the Hamiltonian function
:
H=H
(1)
(J
jfc
o)+AH 1 (J^
^)+.
(*=1
./)
which are connected with the accidentally degenerate motions of the

unperturbed system (A=0), i.e. those for which, as a result of the
choice of integration constants, certain frequencies vanish
OTT
(2)
V=aj^=
(/>=+!.../).
The path fills a region of only s dimensions (s<f) in the case of

the unperturbed system, since the w p 's are constant.
Let us assume that the perturbed motion is connected with a
certain unperturbed motion for which
from the assumption of accidental degeneration that the

Jp 's must have perfectly definite values in the initial motion. The
Jp *'s may be determined if equation (2) be solved for the J p0> s they
appear as functions of the Ja 's. That wp must necessarily have
definite discrete values in the initial motion is certainly an assumption
it is also conceivable that the perturbed motion could be
associated with every system of values w Q of a continuum, but our
p
It follows
argument cannot be applied to

If
we assume,
this case.
therefore, that only certain
initial
motions are
possible, the J p *'s and w p *'s are perfectly definite functions of the
Ja 's so far we do net know wp *(J a ), but this will be found in the
;
course of the investigations.
We now introduce new
variables
f/Wp'-W.
(3)
This
may
V=V-V(J
)'
283
.')-
be accomplished by means of a canonical transformation
with the generator
2. J.'+2[VJp*+fp (V-/)]
(4)
the transformation equations are
's will be equal to the original J a 's, while the w a 's will
from the w a 's only by quantities which are constant in the
unperturbed motion they retain their character of action and angle
's and
's tend to zero with vanishvariables respectively. The
7y p
p
The new J a
differ
ing perturbation.
We
can now develop the Hamiltonian function with respect to
p> ^p
thus obtaining
H=H '+AH
(6)
where (omitting the bar in
H '=H 00 (J a
(7)
From
H/=H 10 (wa
wa
'+A2 H 2 '+
wp *, J
>
(5)
^2!
8w
while the expressions
H 00 H 10
,
are obtained from
H!
... in
*
Q
(6) has now a form
simply by writing J p *, w p instead of Jp, wp
analogous to that of (2) in 46, and may in consequence be dealt
.
(1)
with, to
there.
any degree
of approximation,
by >he method employed
284
There
'.
is
the one difference, that the

^'s do not appear at all in
we make the transformation given by (16), 46,
therefore,
If,
the equations for determining the A/'s and B/'s
become
(10),
46)
mean
value
(</.
It follows
from the second
of these equations that the
bjf vanishes.
Finally, the Hamiltonian function
is
obtained in the form
H=V(JB )+R(J.,
(9)
,,
,,),
where the expansion of K in terms of p rjp commences with quadratic terms. For small values of g
which are all that we need
p TJP
,
consider,
quantum
conditions,
is
separable and gives, as the only solution satisfying the
The perturbed motion has
therefore the
same degree
of periodicity
It is stable (in the ordinary mechanical

only when, the quadratic form in p , rj p in (9) is
as the unperturbed motion.

sense) when,
and
definite.
The condition
&7^<>
(10)
implies a determination of the

3
the
%, which
wp *'s.
For
since the
mean
values of
are pure periodic functions without a constant
VWgf
term, vanish,
it
follows
from
(8)
that
It
This equation implies, however, phase relations for the w *'s.

p
45, since
is, in fact, equation (13),
10 in the present notation
is
identical with
in
45.
45 we considered in great detail the case of one accidentally

we may show finally how it fits in
degenerate degree of freedom
In
with our general considerations of stability.

there
is
equivalent to
2!
H 10 here),
Equation
(5'),
45 (H 2
is,
to a
first
285
approximation, equivalent to
2! dJ,2
for motions in the neighbourhood of solutions of the equation
,
If
-?
is
dJf2
solution
(H 2
positive,
we have
_
~~
in the
neighbourhood of the stable
a minimum) a positive definite quadratic form,
is
whilst in the neighbourhood of the unstable solution (H 2 a maxi#2

? is
mum) the form is indefinite. If
negative, the form is negative
dJf
definite
solution,
maximum) in the neighbourhood of the

indefinite (H 2 a minimum) in the neighbourhood
(H 2
is
stable
of the
unstable solution.
It remains to consider the cases of combinations of different kinds
of degeneration.
It has been
shown that accidental degeneration and
limiting degeneration can be treated in the same way, and so it is

obvious that they do not interfere with one another. In this case
the number of the
variables is simply increased. In addition

77
the sole remaining possibility, a combination of intrinsic degeneration with limiting degeneration, does not, as a rule, involve any
difficulty.
In such a case the secular motions of the intrinsically

first of all calculated and then the procedure
degenerate variables are

of 46 adopted. 1
Special cases, in which, for example, by averaging over the nondegenerate variables, their dependence on the degenerate variables
disappear
We
(e.g.
have now
=0), must of course be examined separately.

40, that the
justified the statement made in
stationary states are to be found chiefly among the particularly

simple types of motion, which can be calculated by comparatively
easy approximate methods.
mathematical tool at hand we shall now proceed to the

calculation of the next simplest atom to hydrogen, that of helium.
We shall show (as mentioned in 40) that the results are not in
agreement with observation but quite apart from this, we consider
With
this
1 The case in which the

degrees of freedom exhibiting limiting degeneration
are at the same time intrinsically degenerate is cfealt with by L. Nordheim,
Zeitechr.f. Physik, vol. xvii, p. 316, 1923.
286
that working out this example is a necessary preliminary to any

attempt to discover the true principles of quantum mechanics.
The Normal
48.
State of the
Helium Atom
According to 32, two one-quantum electron orbits are present in

helium in its normal state. Our problem is to investigate their
possible arrangements in the atom.
We shall take the unperturbed motion to be one in which the
electrons are only subject to the action of the nucleus, of charge
Let the angle and action variables of the first electron be w l9
Ze.
w 2 w3
Jj, J 2 J 3 , and let us distinguish by a dash the corresponding quantities for the second electron. The energy of the unper,
turbed motion
is
then
where
The perturbation function
is
the mutual potential energy of the
electrons
AH 1=
(2)
where
V(x-x')*+(y-y')*+(z-sf)*
denotes the distance between the electrons and
(x
=:
ft
y', z'),
their respective cartesian co-ordinates in
(x, y, z),
any co-ordinate
system with the nucleus as
The expansions
origin.
of the cartesian co-ordinates as functions of the
angle variables (to be calculated from (26), 22) must now be introduced, to provide a starting-point for the calculation of the perturbations. In this connection, however, there is one point to be borne
In the unperturbed Kepler motion (without taking account
in mind.
of the variation in mass) only Jj is fixed by the quantum theory,

whilst J 2 i.e. the eccentricity, remains arbitrary ; in the relativistic
,
Kepler motion, J 2
orbit,
J 2 =J 1 =h.
is
also to be quantised and, for a one-quantum

shall not take account quantitatively of the
We
relativistic variation of
orbit of each electron
is
mass, but we shall assume that the initial

circular with limiting degeneration Ji=A,
J 2 =h.
The unperturbed system consists therefore of two circular orbits
of the same size. In addition to the double limiting degeneration
due to the circular orbfys, we have also a double intrinsic degeneration, arising from the fact that the planes of the two orbits are
287
fixed, and in addition we have an accidental degeneration, since the

rotation frequencies of the two electrons are equal.
By the principle of conservation of angular momentum, the inter-
action of the
two electrons must leave
still
one intrinsic degeneration
(the difference of the longitudes of the nodes of the two orbits on

the invariable plane remains zero). The line of nodes, however,
processes uniformly about the axis of the resultant angular momenas long as we confine our attention to secular perturbations,
tum
the latter makes the same angle with the angular momentum
vectors of the two electron orbits. Limiting degeneration also persists in the perturbed motion (by the argument of
46). The
same
is
true
turbed motion
47)
will,
of
the accidental degeneration.
The
per-
however, only be related to those unperturbed
motions for which the two electrons have some quite definite phase
relations.
In this special state the mutual energy of the electrons will have
a stationary value. It is evident, on visualising the motion, that this
will be the case only if the electrons are as far apart as possible at
every instant, that is, if they are always in the same meridional
plane passing through the axis of the angular momentum.
This almost self-evident result may be arrived at analytically.
In this connection we must
first of all
choose the variables of the
unperturbed motion, so that they can be separated into those which

are degenerate and those which are non-degenerate.
The
limiting degeneration
jY--j 2 '=o
the transformation (which we shall only
j.-jô,
necessitates
first
give for the
electron)
COS
In what follows we shall again omit the bars over w and J x

is then the angular distance of the electron in its orbit from the
and 77 are zero in the unperturbed motion.
line of nodes
:
The accidental degeneration

transformation
t^tax-toi',
or,
requires
the following canonical
solved for the
new
variables,
Ji'=i(Ii-3Ii'),
288
Ii=Ji+J/,
(3')
'
'
w w3 J3
and J 3 depends on the

take
the (x y)- and (x' y')of
the
If
we
co-ordinate
position
system.
The geometrical
significance of
39
planes in the invariable plane of the system (elimination of the lines

'
of nodes), J 3 +J 3 is the total angular momentum and w 3 w 3 '=$.
Since the energy of the perturbed motion can depend only on the
combination J 3 +J 3 ', we
may
write
(4)
so that
J.
his'
In order to calculate the phase

relations in the initial motion we
have to express the perturbation

(2) in terms of the vari-
function
ables toi,
(5)
iti 3 ,
<t
lt
|/, | 3
simple geometrical treatment
gives
FIG. 39.
to/,
(fig.
39)
X~XQ cos
sn
cos
?/=^ sin
cos
cos
where X Q and y are the rectangular co-ordinates of the electron in

nodal line is the # -axis) and i is the inclination of the
its orbit (the
orbital plane to the (z^)-plane.
We have
(6)
For x
y 9 we have
,
=a COS 277^!
=a sin 27710!,
(7)
II
The perturbation function

(8)
where
is
AH 1=
now
(9)
COS
+W) COS
277(111!
-f-sin 27r(itr 1
= (1p
faj 8
does not appear
2
)
+ii
477^1^ cos
)
sin
cos
it is
a cyclic variable, and
angular momentum, is constant.

We must now average the perturbation
turbed motion
289
Jf 3 ,
the resultant
function over the unper-
XfL 1
(10)
= -^ f
tol
and determine the constant value which to/ has

unperturbed motion from
in the case of the
This equation takes the form
and is satisfied only if p0, or if for/ =|(î w^) has one of the values
or | (0 and
are equivalent, as they give the same configuration).
would
lead
to J 3 =0 the two electrons would revolve in the
p~Q
same circle in opposite directions, and this case must be excluded.
In the case taj'^J the electrons will collide on the nodal line each
period. The only remaining possibility is iti/rrÔ, for which the two
;
electrons pass simultaneously through their ascending nodes.

lie at each instant in the same meridian
They
then
plane through the axis of angular momentum.

Let us now introduce the quantum conditions.
In the perturbed motion J' remains zero

f^
to be put equal to 2A, and for J[ 3 we have
;
is
the values 2A,

be equal to 1,
the case
A,
correspondingly,
will
As already mentioned,
can be rejected
of the helium atom
y=0
plane model
or
J, or 0.
^=1 gives a
p=% gives
;
a spatial model, in which the normals to the

electron orbits are inclined to one another at
FIG. 40.
an angle of 120 (fig. 40 shows this case).
The plane model is the He-model first proposed by Bohr. 1 The
1
K. Bohr, Phil Mag.,
vol. xxvi, p. 476, 1913.
19
290
two
electrons are situated at the extremities of a diameter of the
orbit.
moves
The problem reduces to a one-body problem
each electron
in a field of force with potential
4r
r
It describes a Kepler
motion of energy
so that the energy of the whole
atom becomes
W=-2cKA(Z-i)
(11)
In the special case of helium
2
.
(Z=2)
W=-VdM.
(12)
This enables the energy to be calculated which is necessary for removal of the first electron, since after its separation the atom must
have the normal state of ionised helium with energy
The energy
difference
W =
(13)
taL
gives the work done in separating the

energy of the neutral helium atom.
To
first electron,
or the ionisation
calculate the ionisation potential 13-53 volts has to be subcRh of the hydrogen atom it follows that
stituted for the energy
ton>
=28-75
volts.
not in agreement with observation, the method of

electron impact giving the value
This value
is
(14)
lon>
=24-6
Although the motion so found
volts. 1
the equations of motion

not the limiting case of a
satisfies
and the quantum conditions, yet

and is therefore not stable. Applying the result obtained
in 45 for an accidentally degenerate degree of freedom, the motion
it is
libration
__ _
with phase relations
is
only stable
if
maximum for it. Here Hj has obviously a minimum and

hence the numerator a maximum, whilst the denominator (as we
has a
have shown in
45)
is
negative.
1 J.
Franck, Zeitachr. f. Phyaik, vol.
______
xi, p. 155, 1922.
_____
291
This last difficulty alone would not definitely point to the incorrectness of our model, since it is not known if the ordinary
The disstability conditions are valid in the quantum theory.
crepancy between the calculated and observed values of the ionisation potential shows, however, that the model is not correct.
The spatial model was likewise proposed by Bohr and investigated
1
by Kramers. Here we shall merely calculate the energy
approximation. The energy of the unperturbed motion is
in detail
first
where
R is the Rydberg frequency.
perturbation energy
l
is,
by
=AH 1=
The
to
approximation to the
first
(10),
f ,
2
a V2Jo
JoV(l+;> ) +(l-
or
where
VI
47rJ
sin 2
sin 2
\jj
K is the complete elliptic integral of the first kind

/
In our case
V1
i=- and K=2-157. 2
sin2 i sin2
iff
It follows that
WÔ-687
and to
this
-=l-373cR/*Z.
a
approximation the total energy
W
for
is
given by
cR/K2Z -l-373Z)
Z=2,
W=-5-254cRA.
(15)
We
cannot expect this first approximation to be very accurate,

since at times the perturbing force attains half the value of the force
due to the nucleus. Kramers has carried out the calculation with
greater accuracy
and
finds
W=-5-525cRA.
(16)
l525cRA must therefore be expended to liberate

ionisation potential is 2O63 volts. This is
the
and
Energy equivalent to
the electron,
almost 4 volts too small.
1
H. A. Kramers, Zeitachr. /. Physik, vol. xiii, p. 312, 1923 ; also J. H.
Phys. Rev., vol. xxi, p. 372, 1923.
8
Jahnke-Emde, Funktionentafeln, p. 57, Leipzig and Berlin, 1909.
van Vleck,
292
In addition, the motion of this molecule is unstable, as

in the same way as for the plane model.
may
be
shown
We find, then, that a systematic application of the theory of perturbations does not lead to a satisfactory model of the normal
helium atom. It might be supposed that the failure of our method
was due to the fact that we are dealing here with the normal state,
where several electrons move in equivalent orbits, and that a better
result would be anticipated in the case of the excited states, where
the main characteristics of the spectra are reproduced by the quantum theory in the form used here. We shall now show that this
again
is
not the case.
The Excited Helium Atom
49.
Before proceeding to calculate the excited states of the helium
atom we may mention a few facts about the helium spectrum.

The terms consist of two partial systems which do not combine with
one another. Both are approximately hydrogen-like one consists
of singlets, and gives rise to the so-called parhelium spectrum
this also includes the normal state. The other component system
yields the orthohelium spectrum, and consists (apart from the simple
s-terms) of very close doublets. The lowest orthohelium term is
;
(according to its effective quantum number) a 2 1 -term. Since the

corresponding state cannot pass into the normal state with emission
of radiation, it has a particularly long life, or, to use Pranck's expression, it is metastable.
The
transition
from the normal atom to
this
metastable state can be brought about by electron impact. 1

We shall now investigate the highly excited orbits of the helium
atom on the basis of the theory of perturbations, by which we

the external orbits which can be occupied by an electron
added to a helium
first
We
ion.
electron in the ion
shall
is circular.
assume that the orbit of the

Our problem is to investigate
those types of orbits for which the inner

would move in a one-quantum circle.
In this connection
it is
of the outer electron, or
mean
when
electron,
if
unperturbed,
convenient to choose the reciprocal radius

some quantity connected with it, as the
1
J. Franck and F. Reiche, Zeitschr. f. Physik, vol. i, p. 154, 1920.
According
to measurements of H. Schuler, Natururissenschaflen, vol. xii, p. 579, 1924, the
shows
the
two
of
Li+
likewise
corresponding systems of terms (see further
spectrum
Y. Sugiura, Jour, de Physique, Ser. 6, vol. vi, p. 323, 1925; S. Werner, Nature,
vol. cxv, p. 191; vol. cxvi, f. 574, 1925; vol. cxviii, p. 154, 1926; H. Schuler,
Zeitschr. f. Physik, vol. xxxvii, p. 568, 1926).
Moreover, M. Morand (Comptes
Rendus, vol. clxxviii, p. 1897, 1925) has found a new spectrum of neutral Li which
he ascribes to the metastable state of the Li+ core (corresponding to the lowest
level of orthohelium).
"
293
"
A in calculating the perturbation, for the farther

more will the motion of the inner
away
"
electron resemble the
unperturbed motion.'* We shall take into
account the relativistic variation of mass.
If we denote the polar co-ordinates of the outer electron by r, 6, <f>,
those of the inner electron by r', 0', <', and the conjugated momenta
the Hamiltonian function of the three-body problem
by Pr
JV>
of the helium type has the form
small
parameter
the
"
outer
"
electron, the
^r* sin 02m\

2
62
r'
r'
r'
sin2 0'
Z6 Z
2
e*
VV
+r'
2rr'[cos
cos 0'+sin
sin 6' cos
0'
(<
+relativity terms.
is the
and
Let us resolve this function into
1} where
Hamiltonian function of the (non-relativistic) Kepler motion of the
inner electron and H! the remaining part of the above expression.
After calculating the unperturbed motion of the inner electron,
we can find the secular motions of the remaining variables by introducing a new Hamiltonian function, the mean value of x taken over
the unperturbed motion of the inner electron. The integration of
the corresponding Hamilton- Jacobi equation is again performed by
the methods of the theory of perturbations.

We can decrease the number of degrees of freedom in the problem
by an application of the theorem of the conservation of angular
momentum
(elimination of the nodes).

p-jlar axis of the co-ordinate system be takenjui the direction of the resultant angular momentum P=3f 3 /27r, the angular
If
the
separation of the line of nodes from a fixed line in the invariable

plane is a cyclic variable conjugate to P. For the other co-ordinates
let us take the radius vector r of the outer electron and the conju-
gate momentum p r together with the angular separation t/r of the

outer electron from the line of nodes and the conjugate momentum
,
finally
we
electron,
also require the variables
where
(as before)
tum number, w 2', J a
'
w^, J/
w^,
wz Jx J2
',
',
'
of the inner
correspond to the principal quan-
to the subsidiary
quantum number.
THE MECHANICS OB THE ATOM
294
Since the initial motion of the inner electron exhibits limiting

degeneration, it is convenient to replace the variables tu/, w 2 ', J/,
We
'
J 2 by other
variables.
therefore perform the canonical trans-
formation
(2)
/
)
_j
cos
2nw 2
'
9
and then omit the bars once again.
We shall now calculate the mean value of H x in these new variables.

At the same time we
shall develop
H!
and powers
in terms of spherical harand 77.

shall stop
We
of
in powers of 1/r,
it appears that this approximation
after terms in 1/r 3
and 77.
to taking into account terms linear in
i.e.
monics,
is
equivalent
We have now
W=
(3)
and
W,=H
+relativity terms,
where aH stands
and A 2
for the
hydrogen radius, and evaluation gives for
We have
The
neglected terms of degree higher than the
partial differential equation
H^const.
first
is
in
and
77.
not separable.
be resolved into terms of different orders of

it
can
be
/iealt with by the methods of the theory of
magnitude,
Let
us
perturbations.
put
Since, however, it
may
295*
H^
(6)
where
H =A
2
It
is
~- +relativity terms.
r3
easy to see that the relativistic terms are small compared with
1^2, so that our expansion
is
legitimate.
We
w
l9
must now introduce into H! the angle and action variables

w 2 J l9 J 2 of the unperturbed Kepler motion of the outer electron,
,
We shall, however, replace w^ by the

represented by the term
true anomaly
which is connected with w l by the equation
.
XQV
^
x7/O
'
(cf. (18), (7'),
also
J
\
l'"~~"
and (8)-(ll),
put ^ 2 =27rM> 2
interest,
(XCD-i
T a 7i
we obtain
If
^x-v~
\a*
22 fr here=7r+^ of (18), 22) let us

we take Ji=h, which is the only case of
;
ticos
(+-f
sin
(Z-l)cEA
a is the Sommerfeld fine structure constant a= -r

he
(c/.
33)
the
terms proportional to a2 contain the relativitjr correction for the inner
and outer
electrons.
296
In order to solve our problem we have to apply the method

cussed in
dis-
46.
Let us therefore try to find a function
S^J^+fY+Brf-AxY,
(10)
which introduces variables fo^, $ 19 X, Y, such that H! has no linear

and Y, and is quite independent of to x The terms T 1?
terms in
B 8 B,
of (10) are omitted, since we do
A
8
T|
A,
not require them to this degree of approximation. The transforma-
tion generated
by
(10)
is
The reason why we do not need the function

term independent of and 77.
T1
is
that J^ l has no
Writing for shortness

the method leads to the following equations
o=W
(12)
A.+.A-W
(14)
We
have neglected the terms in (14) which involve

follows from (13) that
1
and from
and from
W,^
*''
by averaging over
(16)
&~
Hence we do not need to
calculate Aj.
be found with the help of
(8) (cf.
this
(14)
77.
It
'
991**
and
22).
wa
for
=?j=0,
The mean values may
easily
We obtain from (9) and (15)
THEOBY OF PERTURBATIONS
297
whence
3
l
VÂVAIA 1-. cos
t
|,a-J tt- A
srn
It follows that
and
finally
__.
2
4Z2 J 18
We notice that in averaging over w

on w 2 has of itself vanished w 2
J 2 remains an action variable.
:
The quantum conditions are

t
is
in
and
^2 the dependence
cyclic to this approximation
and
therefore
J 2 =| 2 =M,
=nh,
J,=jA.
The relativistic terms are of no practical importance (we have

taken them into consideration throughout only to show that they
1
give rise to no difficulties). If we omit them, the energy
1
W =H
may
be expressed as a Kydberg
(20)
(20)
series formula.
It
is
found that
WWl
where
2k
Writing j~k+p, and expanding in powers of -, the result
fc
is
298
The
total energy of the excited helium
atom becomes
W=
(23)
(+8)
Z=2. This solves our problem. 1

The formula (20) must lead to the spectrum
with
can have the values 1,0,
1, it
Their Rydberg corrections would be (for
P= 0:
(24)
of helium.
Since
must give three systems of terms.
Z=2)
8 =S7IS'
p=-l: S=
The following table gives the values
them the empirical values of 8
of 8 for k =2, 3, 4,
and below
Comparison of the two shows clearly that the theoretical values

do not agree with the empirical values.
We may therefore conclude that the systematic application of the

principles of the quantum theory proposed in the second chapter,
namely, the calculation of the motion according to the principles
of classical mechanics, and the selection of the stationary states
from these by determining the action variables as integral multiples
of Planck's constant, gives results in agreement with experiment
only in those cases where the motion of a single electron is conit fails even in the treatment of the motion of the two
sidered
electrons in the helium atom.
;
This
is
not surprising, for the principles used are not really con-
on the one hand the classical
differential relation is replaced

in
the
of
the Bohr frequency condition,
a
difference
relation,
shape
by
sistent
1
The general solution pi this problem without restriction to circular orbits
of the inner electron has Seen obtained by M. Born and W. Heisenberg, Zeitschr.
/. Physik, vol. xvi, p. 229, 1923.
in describing the interaction of
299
an atom with radiation, while on
the other hand the classical differential relations have hitherto been
in dealing with the interaction of several electrons.

complete systematic transformation of the classical mechanics into
a discontinuous mechanics of the atom is the goal towards which
employed
the
quantum theory
strives.
APPENDIX
Two Theorems
I.
in the Theory of
Numbers
If A is an irrational number, two integers r and r'

from zero can be chosen so that (r+r'X) is arbitrarily small.
THEOREM.
(a)
differing
On the unit distance OE, imagine the distances OT? l9

measured out from 0, their lengths being A [A], 2A
[2A] ...([#] denotes here the greatest integer which is not greater
than x). It follows from the irrationality of A that none of the points
coincide. Further, since they are all situated on the
0, P 1? P 2
unit length they must have a point of concentration P, in the neighbourhood of which there are points P a and
T of the series, between which the distance is smaller than a given quantity 8. This
Proof.
OP 2
P^
separation, however,
and
r
is
;
is
given by
smaller than an integer
by
r'A.
Let
this
whole number be
then
|T+r'A|<S.
(6)
The
straight
trajectory in the space of the angle variables w is a

Without loss of generality we can choose a point on
line.
it will then be seen that the direction

the trajectory as origin
cosines of the trajectory are proportional to the frequencies v l9
vf
We have then the
v%
;
THEOREM.
If no degeneration is present, then for any given

in
the
w-space it is always possible to find an equivalent
point
to
which
the trajectory approaches indefinitely close.
point
If we confine the trajectory to a single cube, by replacing each
point of the trajectory by the equivalent point in the unit cube, we

can state the theorem in the following form
THEOREM. The trajectory approaches infinitely close to every
:
point of the unit cube.

This corresponds ô the following theorem in the theory of
numbers
300
APPENDIX
If
a n and any number b are given, n

numbers a l
rn can always be found so that
irrational
integers r l
()-6=r 1a 1 +
differs
We
way
301
+rn a n -b
from an integer by an arbitrarily small amount.

can prove the theorem for the trajectory in the following
1
be the origin and
Let
OE^ OE 2
OE,
unit lengths along the
axes of the (w l9 w 2
^-co-ordinate system.
be the points of intersection of the
.
Let
PI,
Pa
path, confined to the unit cube, with

the (/ l)-dimensional surfaces bounding the unit cube, which intersect in
OE OE 2
1?
OE
Let
f.
P and
be
Since the direction cosines
identical.
none of these
they have at least
are incommensurable
points
Pw
coincide
one limit point in each of the bounding

surfaces perpendicular to the axes. In
each of these (/
FIG. 41.
l)-dimensional sur-
an infinite number of vectors Pm Pm+n

whose magnitudes are less than a given number S.
We must be quite clear as to the distribution of the points of
intersection on the bounding surfaces, each of which is perpendicular
to one of the axes OEj .... For this purpose, let us consider any
one of the surfaces, say that which is perpendicular to OE/. Of the
series of points of intersection Pj, P 2
., let P^. be the first which
faces, there is therefore
bounding surface (a
we should have degeneration).
falls in this
a finite number, since otherwise

We may suppose that the vectors
is
PwPw+n * n fche bounding surface are drawn from f and so we arrive

new points of our series, Qi, Q 2
We have now to show that these do not all lie in one (/ 2)ff)
at
dimensional space passing through P^.

directly,
by
first
assuming
it
to be true,
We
shall
prove this
in-
and showing that
this leads
(*=1
./-I)
to a contradiction.
The point P^ has the co-ordinates
in the bounding surface under consideration.

1
other points
F. Lettenmeyer (Proc. London Math. Soc.

theorem in the theory of numbers.
Appended to the proof by
xxi, p. 306, 1923) of this
For/
(2), vol.
302
P^,
Pa.
points
P 9M
all lie
""
vi_r
L
Vf
or, after
we
of the Q-series
on a surface of /
have,
if
P, and the (/I) other
2 dimensions,
=0.
vf
v/-i"i
- r^!-^
"
vi~|
Vfj
^/
a simple rearrangement,
Vf
__Vf
=0.
Since no integral relation
Tl~+T 2 V-+
Vf
may
exist,
must vanish
If we divide the
we obtain
first
+T/_ '^+T/ -0
1
Vf
apart from the case
efficient of -i
when
all
the r's are zero, the co-
row by
and proceed to the
limit
=0.
APPENDIX
303
J/
The
coefficient of
in this expression
must vanish.
If
we
divide
"/
row by x%
must have
first
and allow x 2 to tend to
oo
it will
be seen that we
Vf
Vf
=0.
we may continue
this process until

r~
we
arrive at the relation
=0.
This contradicts, however, the irrationality of

If the points of the Q-series
do not
dimensional space passing through P^,
all lie
-^
1
.
in one linear (/ 2)1 of the
we can pick out/
which form an (/ l)-dimensional (/ l)-edge. If

1 vectors to the end point of each of these
all the/
vectors, and continue this process, we can cover the whole (/!)dimensional surface of the unit cube perpendicular to OE, with a
net of cells, the sides of which are smaller than 8. Evidently the
F^Q,
vectors
we again
attach
same
is true for those boundaries perpendicular to the other OE,-.

This shows, however, that the points of intersection of the trajectory fill the bounding surfaces completely, and hence the trajectory
approaches infinitely close to every point of the unit cube.
n. Elementary and Complex Integration

Integrals of the form
,
where
is a rational function of the given argument, are of frequent

occurrence in our problems. We have to deal with the definite
integral, taken over a libration of x, in calculating the energy as a
function of the J's, and with the indefinite form in calculating, for
example, the angle variables.
The
means
indefinite
:
if e l
and
integration
may
be performed by elementary
under
e a ( e i >e 2) denote the roots of the expression
304
the square root sign, this expression takes the form (neglecting the
factor
A)
2
on making the substitution
f2
p1
dx
cos
The
integral then
becomes
""
sm
-~
cos
cos
the integral of a rational function of sin i/t and cos if/, which
in every case may be reduced to the integral of a rational function of
u by the substitution w=tan |0, or alternatively, if the integrand is
which
is
an even function
of its argument, by the substitution

us consider the following examples
:
jVa
1.
The
substitution
(1)
a 2 cos 2
I
xa
fidtft=
sin
i//
x*dx.
gives
|(l+cos
4J
2iff)d2iff== a
-H
x
= -If a2 sin- 1 -+va
x2
2L
sin
[_2
1
.
The definite integral taken over one libration of x is
$Va 2
(2)
x2dx=a 2
cos 2 if/diff=7ra 2
-dx.
By the
substitutions
f
J
#=sin
JL
sin 2
0,
w=tan
^0=1
J1
The integrand can be resolved
11
0,
+w2 (l
we
obtain
'
a) 1
+u2
into partial fractions
a 1+u*
1
,
w=tan
iff.
Let
AI
APPENDIX
Hence the
indefinite integral is
fl
tan"1 uqp
a
1
- tan"1 w-t
w
x.
tan"1
Va
j?__.
if
Vl
x2 be
log
uVl
luVa
littVa
^
where,
305
positive, the value H
a) for a <: 1,
r=
l^puVal
== be
Vlx*
1
for aj>
a^l,
~~ 1,
is
to
substituted
..
for u.
In the case when a<l the integral over a libration of x

JT
Vl - x
2tr
cos
C
fc
r*=
lax
ax
Jo
<Pl1
If it is
Jo 1
2
*
,,
t/r
2?r
7T
di/j=
rY-d0=
2
a sin
iff
/f
/,
is
VI a).
(1
(1-Vl-a).
only necessary to find the values of the definite integral
J=#R(z, V-Ax*+2Rx-C)dx,
the method of complex integration is usually the most convenient.
If x be represented in the complex plane, the function R can be
pictured on a Riemann surface of two sheets with branch points at
the roots e l and e 2 (e 1 >e 2 ) of the radicand. The path of integration
encloses the line joining the two roots. If it goes from e 2 to e x
(dx>0) in that sheet of the surface where the root is positive, it goes
from
6 X to e 2 (dx<0) in the sheet
example,
fig.
with the negative root
(see, for
42).
The simplest way of evaluating the integral is to distort the path

of integration and separate it into individual contours, each of which
encloses one pole of the function. With the direction of rotation
indicated in fig. 42, J is then equal to the negative sum of the
residues of the integrand in these poles (the residue is 2ni times the
coefficient of l/(xa) in the Laurent expansion in the neighbourhood
of the pole a
pole a)
we
will use the
symbol Res
for the residue at the
Let us consider a few types of
Group
integrals.
1.
J=
The constants A, B, C are supposed
positive.
If real roots exist
tive
306
The only
real axis.
3=00
possible poles of the integrand are at
x=0
and
We have therefore
J= The diagrams of the original and deformed paths of integration in

this instance are clearly shown in fig. 42, in which the pole 05=00 is
represented as if it were at a finite distance. Outside the range e ly
e2
on the
+i from
real axis, the root is purely imaginary,

and
i from
oo to e 2
,
e l to oo
and has the sign
FIG. 42.
We
calculate Res> as the Res of the integrand of the integral

arising from the substitution y=l/x ; since in the representation of
the x-surface on the y-surface, the direction in which the path of
integration
is
Resoo
traversed remains unaltered,
[x*(V-Ax*+2Bx-Cy]
= -Res
The root has
(a)
sign
a=-l,
we have
from
l/e 2 to
y=oo and +i from

,
oo to l/er
=+1:
Taking account of the above determination of
sign, the
expansions
of the integrand necessary for the calculation of the residues at o?=0
and
y=0 are
V5
and
y
respectively.
It follows therefore that
Res ao
27T
VA
APPENDIX
307
Ji= (j>- V(6)
For aj=oo the
integral
integrand
~
that
For 35=0, the expansion of the
is
regular.
is
I/
is
T>
CVC
and
xy.2
(6)
B
CVC
C\-
a=-
(c)
integral is regular at #=0.

ing integrand for y=l/x=0 is
The
=H
-o
y*LiVA.
that
B
=VH
iAVA
1 /
.(3
2t\
The expansion
B2
A VA
2
of the correspond-
n)v2 +
AVA/
is
B2
consequently
T
*~~
V-Ax*+2Ex-CJ
(7)
VA\A
Group 2
r
( a) CD
A/
Vla;~2
-r
dx.
We can distinguish two'possible cases.
308
2
poles of the integrand given by the roots of 1 ax
1
lie outside the path of integration surrounding the zero points
the
real
lie
on
of the roots (branch points of the integrand)
they
1.
a<l.
The
axis for
is
0<a<l, and on the imaginary
composed
axis for
a<0.
The
integral
of the residues at
x=.V
and #=oo
The root is positive and imaginary on the positive real axis, and
it is positive and
negative and imaginary on the negative real axis
and
real on the negative imaginary axis,
negative and real on the
;
positive imaginary axis.
Taking these signs into account, the expan-
sion of the integrand at its poles
commences with
&
\l
The
residues in both poles are the same, viz.
77
The contribution
of the contour about
x =00 works out to be
Since the root is positive and imaginary for positive real values in
the neighbourhood of zero, the expansion of the function starts with
ay
277
This gives for the required contribution

277.,
2.
a>l.
The
poles
and
a
finally
,-
./ -fall in the interval
1,
+1)
of the real
and lie therefore inside the path of integration. The integrand

does not remain integrable at them, so that this case must be
excluded.
axis
APPENDIX
309
(&)
with
/(s)=(A-*)(s-B),
F(aO=/(aO-ACte.
Let A, B, C be positive and real, A>B, and C chosen so that F(x) can
assume positive values. The roots a, j8 of F(x) are then real and lie
between A and B.
The integrand
becomes
possesses simple branch points at a
but remains integrable.
infinite there,
and
]8
Simple poles
it
lie
FIG. 43.
at
A and B.
integral.
Again, a circulation about x =00 will contribute to the

signs of the roots are given in fig. 43. In the neigh-
The
bourhood of
A the expansion of the integrand commences with

X
*Vc
in the vicinity of
The
with
residues axe therefore
"
ResA
=--,
Using the substitution

OB*
__
es
p~
yl/xwQ find
1-ABy2
_ 1)(1 _ By)
o|_~ (A2/
__
1
'
"I
v^-l)(l-By)-ACtJ'
where the root for positive real values of y in the neighbourhood of

zero has the sign +i. The expansion commences therefore with
,
and
Hence
(9)
f(x)V$(x)
310
In conclusion we will consider one or two other integrals of the
form
V - Ax* +2Bz-C +Xf(x))dx,

where \f(x) represents a correction term. Under these circumstances
the positions of the branch points are not essentially different from
those in the integrals of group 1, and the previous figures and determinations of sign and paths of integration remain the same.
In order to carry out the integration we have to expand the
integrand in powers of the factor A of the correction term, and in this
connection it should be noticed that the expansion must be valid
whole path of integration, so that in this case the path of

integration must first of all be suitably deformed. Should new
branch points be added on account of the correction term, they must
be avoided by the deformed path of integration.
The integration may then be carried out by the same process as
for the
before, since for the individual terms only the branch points e l
e 2 , and the poles ce
0, #=oo occur.
Jt
(a)
For
sufficiently small values of
the whole path of integration.

the first order in
the expansion for
Let us
D=0 holds
restrict ourselves to
D
or
BD
J7 =
=(L / -A+2? - 2.* +Dx dx.

*
JV
for
terms of
Hence
(6)
and
APPENDIX
The expansion
of the square root in
Confining ourselves to terms of the
or
/
(11)
J 7 -5
,-\
311
powers of
first
D yields
order in D, this leads to
INDEX
(The numbers
a-rays, 13.
Accidental degeneration, 89, 97,

265 et seq.
Action variable, 45.
Adiabatic hypothesis, 54.
Adiabatic invariance (for one
degree of freedom), 52 et
seq.
(for several degrees
of freedom), 95 et seq.
Alkali metals, spectra, 166

Aluminium atom, 194.
Aluminium spectrum, 164.
Amplitudes,
refer to pages}
Band-head, 118.
spectra, 116 et
tion), 63 et seq.
Band
Band system,
128.
Barium atom,
197.
Bessel functions, 147, 223.

Bohr's frequency condition,
(rota-
7, 11,
14, 59, 98.
et seq.
Bohr's fundamental hypothesis,

14.
Boron atom, 192.

Branch (of a band),
of
correspondence
;
Bergmanii series, 152.

Beryllium atom, 192.
the, 60, 101.
Angle variables, 45
seq.
118.
(for central
orbit), 137.
momentum, 23, 25
(quantisation of the), 104 et
Angular
seq.
155
(of
(of
an
electron), 152,
electrons in
the
molecule), 110, 118
Anomalous Zeeman
et seq.
effect,
168,
212.
Anomaly (eccentric), 142

138; (true), 295.
151
in series,
et seq.
Atomic core, 130, 151, 183,

Atomic number, 13, 177.
Atomic structure, 12 et seq.
Atomic volumes, 196 et seq.
187.
Carbon atom, 193.

Cathode rays, 13.
Celestial mechanics, 247.
Central field, 130 et seq., 151 et seq.
Centre of gravity (electrical), 145.
Characteristic radiation, 174 et
seq.
Chemistry and atomic structure,

180 et seq.
Commensurability of frequencies,
77, 81, 83 et seq., 91 et seq., 97.
Complex integration, 305 et seq.
0-rays, 12.
Band
et
seq.
Aufbauprinzip, 183.
Balmer
197.
Caesium atom, 197.

Calcium atom, 194.
Canal rays, 12.
Canonical equations, 20 et seq.
Canonical transformations, 28
(mean),
priori probability, 9.
Argon atom, 194.

Arrangement of spectra
Cadmium atom,
Conditionally
series, 149, 206.
periodic
81.
groups, 128.
Conjugate variables, 21.

313
systems,
314
Continuous X-ray spectrum, 174.

Convergency of perturbation cal;
(spectrum),
184, 188.
Core of the atom, 130, 151, 183,

187.
Core
radii, 187.
Correspondence principle, 8, 9
(for one degree of freedom),
60 et seq.
(for several degrees of freedom), 99 et seq.}
(in the Stark effect), 220 et seq.
Coulomb field, 131, 139 et seq.
;
Coupling of oscillation and rotation in molecules, 122 et seq.

Coupling of several electrons, 247
et seq.
Crossed
electric
fields,
235
and
magnetic
et seq.
Cyanogen bands, 129.

Cyclic variables, 24 et
seq.,
102
Degenerate systems, 89
seq.
et seq.,
(perturbations
107, 261
97
of),
et seq.
Degenerate variables, 92.

Degeneration (intrinsic), 89, 261
et
tion), 6
(in
mechanics), 22
et seq.
4.
Energy quanta,
Equations of motion, 17.

External orbits of series electron,
155 et seq.
Failure of
131.
classical
mechanics,
Fall, free, 40.
Flywheel in top, III et seq.

Foundations of atomic mechanics,
1 et seq.
Frequency condition,
7,
11,
14,
59, 98.
Fundamental
series,
152,
154,
166.
Fundamental system
of periods,
73.
Fundamental
vibration, 61.
(accidental), 89, 97,

seq.\
(limiting),
275
Gallium atom, 196.

Generator (of a transformation),
et seq.
Degree of freedom,
Deslandre's
an atomic
et seq.
core,
166.
265
of
Deformation of the atomic
et seq.
moment
system, 60, 100.

Electron, 12.
Electron bombardment, 15, 59.
Elliptic co-ordinates, 241 et seq.
Energy, conservation of (for radia-
Frequency, 2, 47
(correspondence for the), 60 et seq., 90
et seq.
et
(for the photoelectric effect), 7 et seq., 174.
Electric
culations, 253, 255.
Copper (atom), 196
Einstein's law
20.
band formula,
64,
116.
Difference quotient, 61, 100.

Double bands, 127.
Dulong and Petit's law, 5, 71.

Dumb-bell (molecular model), 63
et seq.
Eccentric anomaly, 142.

Effective nuclear charge, 153.
Effective quantum number, 157,
164, 184.
Ehrenfest's adiabatic hypothesis,
54.
31.
Gold atom, 197.

h (Planck's Constant),
Half -integral k, 168.
3.
Halogen hydrides, 127.

Hamiltonian function, 21.
Hamilton - Jacobi
differential
equation, 36 et seq.
Hamilton- Jacobi theory, 17 et seq.
Hamilton's Principle, 17.
Harmonic oscillator, 2, 34, 50, 62
;
(spatial),
Heat
77
radiation,
et seq.,
1 et seq.
80, 84.
INDEX
Helium
atom,
286
states), 292
state),
191
et
seq.
315
(normal
Limiting degeneration, 275
(excited
Lissajous figure, 77, 81.
et seq.
Lithium atom, 192.
et seq.
Helium spark spectrum, 150.

Hydrogen atom, 148, 191
series, 150, 206.
Lyman
(in
electric field), 212 et seq.

(in
crossed electric and magnetic
;
235 et seq.
Hydrogen molecular ion, 245.
Hydrogen spectrum, 15, 149.
Hydrogen-type spectra, 147 et seq.
fields),
Indium atom,
197.
Magnesium atom, 194.

Many-body problem, 130,
247.
Mean
Kepler
values
the
for
motion, 143
Molecular heats
et seq.
(solids), 5, 71
(diatomic gases), 65 et seq.
Molecular models, 63, 110, 117 et
;
seq.
Integral invariants, 35.

Integration (elementary), 303
seq.
(complex), 305 et seq.
Molecule, diatomic, 63
et
(correspondence of),
62, 101
(in the Stark effect),
220 et seq.
Interaction (between matter and
9
2,
6,
(of
radiation),
;
et seq.,
110,
et seq.
Momentum,
Intensities
several electrons), 247.

shell, 196.
Intrinsic degeneration, 89, 261
117
tion
20
17,
of),
25
(conserva-
(angular), 23,
25.
Moseley's law, 14, 177.

Multiplicity of
152, 155.
spectral
terms,
71
Multiply periodic functions,
Intermediate
et seq.
et
seq.
Multiply periodic systems (separ(general), 86

able), 76 et seq.
;
Ionic radii, 186, 187.

lonisation, work of, 154.
Ions, 13.
et seq.
Negative branch (of a band), 118.

Neon (atom), 193
(spectrum),
;
Jacobi's integral, 23.
Kepler motion, 139

201
tivistic),
185.
et seq. ;
et
seq.
(rela;
(in
parabolic co-ordinates), 219.

Kepler's law (third), 142.
Krypton atom,
196.
Nickel atom, 196.

Niton atom, 197.
Nodes, line of, 137, 232
et seq.,
238
Non-harmonic oscillator, 66 et seq.

125, 257
et seq.
(spatial),
259
et seq.
Normal
154
state,
helium atom), 286
Lagrange's equations, 18, 20.

Lanthanum atom, 197.
Larmor
et seq.,
287.
(of
the
et seq.
Nucleus, 13.
Null branch (of a band), 118, 127.
Null line (of a band), 118, 127,
precession, 210, 236.
Legendre transformation,
20.
Libration centre, 49.

Libration limits, 49 (coincidence
129.
of the), 276.
Libration, motion of, 45, 48

seq.
Limitation, motion
et
Occupation numbers, 198.

131
One-body' problem, 123,
seq.
of, 49.
Orthohelium, 192, 292, 298.
et
316
Oscillations of molecules, 123
et
seq.
Oscillator (harmonic), 2, 34, 50,
62
66
(non-harmonic),
seq.,
125, 257
et seq. ;
77 et seq.,
et
(spatial
80, 84 ;
Positive branch of a band, 118.

Positive rays, 12.
Potassium atom, 194, 200.
Principal
151 ;
terms
183 et
harmonic),
(spatial non-harmonic), 259
136,
(actual values of, for
of
optical
spectra),
seq.
Principal series, 152, 154.

Probability, a priori, 9.
Projection (under gravity), 40, 41.
Pyroelectricity, 70.
et seq.
Overtones, 61, 100.
Oxygen atom,
quantum number,
193.
Palladium atom, 197.

Parabolic co-ordinates, 212.
Parhelium, 192, 292, 298.
Partition function, 3.
Paschen series, 150.

Pendulum, 40, 49 et
Pendulum
orbit
Quantum
conditions, 4,
14 (for
one degree of freedom), 56,

59
(for several degrees of
;
freedom), 98.
seq., 52, 55.
(Pendelbahn),
136, 234.
Quantum number,
tive), 157,
Penetrating orbits, 161, 169
et seq.
Perihelion, rotation of, 139, 158,

205.
Periodic functions (multiply), 71
16
164, 184;
cipal),
136,
values
of,
151
for
(effec-
(prin-
(actual
terms of
optical spectra), 183 et seq.

Quantum transition, 6, 54.
et seq.
Periodic
45
motions,
et
seq.
(multiply), 76 et seq.
Periodic system of the elements,
13, 181 et seq.,
191
60, 100.
et seq.
Radiation, law of,

Radiation, theory
Periodicity, degree of, 92.

Perturbation function, 107.
Perturbation problem, 107.
Perturbations, theory
of,
247
Rare
et
seq.
Perturbations of an intrinsically
degenerate system, 107 et
seq., 261 et seq.
Perturbations of a non-degenerate
system, 249 et seq.
Perturbations, secular, 107 et seq.,
261 et seq.
Phase relations, 268 et seq., 282
2.
Photo-electric effect, 7.
Planck's Constant, 3.
Planck's law of radiation,
3.
of, 1 et seq.
earths, 197.
Rayleigh- Jeans formula, 3, 11.

Relativistic Kepler motion, 201
et seq.
Relativistic resolution of the
and He+
lines,
205
et seq.
Relativity theory, 17, 19, 24.

Relativity, X-ray and optical
doublets, 207.
Resonator,
2, 62.
Ring models, 180.

Ritz correction, 165.
Ritz spectral formula, 161 et seq.
Rosette orbit, 139, 158.
Rotational motion, 45, 48 et seq.
et seq.
Phase space,
Radiating electron, 131, 151, 175.

Radiation from an atomic system,
3.
Platinum atom, 197.

Polarisability (of atom core), 167.
Polarisation (of radiation), 62,
101, 106.
Rotation bands, 64.

Rotation, heats of, 65 et seq.
Rotator, 26, 63 et seq.
Rotators, two coupled (accidental
degeneration), 265 et seq.
INDEX
Kubidium atom, 197, 200.
Rydberg Constant, 148, 151.
Rydberg correction, 160, 165
Subordinate
Term
sequence, 152.
Terms, 152
spectral formula, 160.
number,
quantum
136, 151.
et
et seq.
Rydberg
series, 152, 154.
Subsidiary
seq., 173, 184 et seq.

Rydberg-Ritz spectral formula,
161
317
Theory
of
et seq.
numbers,
theorems,
300.
Scandium atom,
200.
196,
195,
Secular perturbations, 107 et seq.,

261 et seq.
Selection principle, 138, 152, 180.
Separable systems, 76 et seq.

Separation of the variables, 44, 76
et seq.
Serie> electron, 130, 151.

Series spectra, 131, 151 et seq.
Shell structure of atoms, 176, 182,
191 et seq.
Silicon atom, 194.
Silver (atom),
184, 188.
197
(spectrum),
Sodium (atom), 193
(spectrum),
164.
Somrnerfeld's theory of fine structure,
202
et seq.
Space quantisation, 105, 110,
Titanium atom, 196, 200.
Top
(free symmetrical),
26
et seq.
Transformation (canonical), 28
et
(Legendre), 20.
Transition, probability of, 9, 62.
Two bodies, problem of, 123, 131.
Two centres, problem of, 241 et
seq.
seq.
Uniqueness of the J's (in separable systems), 83 et seq.

(in
general), 86 et seq.
;
155,
Variation principle (Hamilton's),
211, 240.
Spatial oscillator (harmonic), 77

et seq.,
80, 84
(non-harmonic), 259 et seq.
(diaSpecific heats (solids), 5, 71
17.
tomic gases), 65.

Spectra (of molecules), 63 et seq.,
Ill et seq., 127 et seq.
(of
the halogen hydrides, infrared), 127 et seq.
(of atoms,
hydrogen type), 147 et seq.
Wave number,
128, 148.
Wien's displacement law, 4, 11.

Wien's law of radiation, 3.
(of
atoms,
non
Xenon atom,
197.
X-ray spectra, 13, 15, 173

X-ray terms, 178 et seq.
et seq.
hydrogen
type), 151 et seq.

Stark effect for hydrogen, 212
et
Yttrium atom,
197, 200.
seq.
Stationary [states,
of
in
field
(symmetrical,
force), 42 et seq.
(free unsymmctrical), 115 et seq.
(with flywheel), 111 et seq.
Transformability, mechanical, 54.
6,
130.
Strontium atom, 197.
11,
14,
52,
Zeeman
effect, 168,
Zinc atom, 196.

Zustandsintegral, 3.
207
et seq.
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OU_1 66524 >

OSMANIA UNIVERSITY LIBRARY

INTERNATIONAL TEXT-BOOKS OF EXACT SCIENCE

N. DA C. ANDRADE, D$c., PH.D.

THE MECHANICS OF THE ATOM

be welcomed by all interested in the subject. The ground covered is

BELL AND SONS, LTD., LONDON, W.C.2

BELL AND SONS, LTD.

Printed in Great Britain by

DEDICATED IN ALL GRATEFULNESS

PREFACE TO THE GERMAN EDITION

given to these lectures which I

delivered in Gottingen during the session 1923-24, was chosen to

term covers that branch of theoretical astronomy which deals with

be argued that the theory is not yet sufficiently developed to justify

have called the

clear in the title, I

the second volume is to contain a closer

only a few hazy indications as to the departures which must be made

among these indications I include Heisenberg's conception of the

Kramers towards a quantum theory of dispersion phenomena as

relating to the application of the theory of perturbations to the

THE MECHANICS OF THE ATOM

not nearly enough for the foundation of a

theoretical problems which

which the most important physical foundations of the new mechanics

is of course unavoidable, but, even in these

Again, with regard to the foundations of the quantum theory, there

however, I leave for the reader to discover by direct comparison.

particular I share the opinion of the Copenhagen investigators, that

my opinion, constitutes the basis

the proof worked out by Hund

English translation of third edition, 1923, by H. L. Brose, Methuen

PREFACE TO THE GERMAN EDITION

AUTHOR'S PREFACE TO THE

SINCE the original appearance

the subject-matter of the projected second volume has already

quantum mechanics which was initiated by Heisenberg, and

mechanics suggested by de Broglie, and brilliantly worked out by

modes of exposition. Many of the theoretical difficulties

that the time

in these circumstances, the appearance of an

not yet arrived

new mechanics can

foundations, without any connection with

development, and doing injustice to the genius of Niels Bohr, to

and to ignore the struggle for clear conceptions

the book which I wish to withdraw.

THE MECHANICS OF THE ATOM

writing of this book have prepared the way

for the critical step

therefore, with a clear conscience that I authorise the English

not elementary, but supposes the reader to have some knowledge

Germany Sommerfeld's Atombau und SpeJctrallinien is much used

who prepared the translation in the first place