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The Theory of Spectra
and
Atomic Constitution
THREE ESSAYS
BY
NIELS BOHR
Professor of Theoretical Physics in the University of Copenhagen

CAMBRIDGE
AT THE UNIVERSITY PRESS
1922
 PRINTED IN GREAT BRITAIN
AT THE CAMBRIDGE UNIVERSITY PRESS
 Collegt
LibrMJT

PREFACE
three
essays which here
appear English in all deal with
THE
the application of the quantum theory to problems of atomic
structure, and refer to the different stages in the development of
this theory.
The first essay " On the spectrum of hydrogen" is a translation of
a Danish address given before the Physical Society of Copenhagen
on the 20th of December 1913, and printed in Fysisk Tidsskrift,
xn. p. 97, 1914. Although this address was delivered at a time
when the formal development of the quantum theory was only at
itsbeginning, the reader will find the general trend of thought
very similar to that expressed in the later addresses, which
form the other two essays. As emphasized at several points the

theory does not attempt an "explanation" in the usual sense of

this word, but only the establishment of a connection between facts
which in the present state of science are unexplained, that is to
say the usual physical conceptions do not offer sufficient basis for
a detailed description.
The second essay "On the series spectra of the elements" is a
translation of a German address given before the Physical Society
of Berlin on the 27th of April 1920, and printed in Zeitschrift fur

Physik, vi. p. 423, 1920. This address falls into two main parts.
The considerations in the first part are closely related to the con-
tents of the first essay especially no use is made of the new
;

formal conceptions established through the later development of

the quantum theory. The second part contains a survey of the
results reached by this development. An
attempt is made to
elucidate the problems by means of a general principle which postu-
lates a formal correspondence between the fundamentally different

conceptions of the classical electrodynamics and those of the

quantum theory. The first germ of this correspondence principle
may be found in the first essay in the deduction of the ex-
pression for the constant of the hydrogen spectrum in terms of
Planck's constant and of the quantities which in Rutherford's

733173
vi PREFACE

atomic model are necessary for the description of the hydrogen

atom.
The third essay "The structure of the atom and the physical
and chemical properties of the elements" is based on a Danish
address, given before a joint meeting of the Physical and Chemical
Societies of Copenhagen on the 18th of October 1921, and printed
in Fysisk Tidsskrift, xix. p. 153, 1921. While the first two essays
form verbal translations of the respective addresses, this essay
differs from the Danish original in certain minor points. Besides
the addition of a few new figures with explanatory text, certain
in the second essay are
passages dealing with problems discussed
left out, and some remarks about recent contributions to the
subject are inserted. Where such insertions have been introduced
will clearly appear from the text.
This essay is divided into
four parts. The first two parts contain a survey of previous results

concerning atomic problems and a short account of the theoretical

ideas of the quantum theory. In the following parts it is shown
how these ideas lead to a view of atomic constitution which seems
to offer an explanation of the observed physical and chemical
properties of the elements, and especially to bring the character-
istic features of the periodic table into close connection with the

interpretation of the optical and high frequency spectra of the

elements.
For the convenience of the reader all three essays are subdivided
into smaller paragraphs, each with a headline. Conforming to the
character of the essays there is, however, no question of anything
like a full account oreven a proportionate treatment of the subject
stated in these headlines, the principal object being to emphasize
certain general views in a freer form than is usual in scientific
treatises or text books. For the same reason no detailed references
to the literature are given, although an attempt is made to mention
the main contributions to the development of the subject. As
regards further information the reader in the case of the second
essay is referred to a larger treatise "On the quantum theory of
line spectra," two parts of which have appeared in the Transactions of
the Copenhagen Academy (D. Kgl. Danske Vidensk. Selsk. Skrifter,
8. Rsekke, iv. 1, 1 and II, 1918), where full references to the literature

may be found. The proposed continuation of this treatise, mentioned

 PREFACE Vll

at several places in the second essay, has for various reasons been

delayed, but in the near future the work will be completed by the
publication of a third part. It is my intention to deal more fully
with the problems discussed in the third essay by a larger syste-
matic account of the application of the quantum theory to atomic
problems, which under preparation.
is

As mentioned both in the beginning and at the end of the

third essay, the considerations which it contains are clearly still

incomplete in character. This holds not only as regards the

elaboration of details, but also as regards the development of the
theoretical ideas. It may be useful once more to emphasize,
that although the word "explanation" has been used more
liberally than for instance in the first essay we are not concerned
with a description of the phenomena, based on a well-defined
physical picture. It may rather be said that hitherto every
progress in the problem of atomic structure has tended to emphasize
the well-known "mysteries" of the quantum theory more and more.
I hope the exposition in these essays is sufficiently clear, never-
theless, to give the reader an impression of the peculiar charm
which the study of atomic physics possesses just on this account.
I wish to express my best thanks to Dr A. D. Udden, University
of Pennsylvania, who has undertaken the translation of the
original addresses into English, and to Mr C. D. Ellis, Trinity

College, Cambridge, who has looked through the manuscript and

suggested many valuable improvements in the exposition of the

subject.
N. BOHR.
COPENHAGEN,
May 1922.
 CONTENTS
ESSAY I

ON THE SPECTRUM OF HYDROGEN

PAGE
Empirical Spectral Laws 1

Laws of Temperature Radiation 4

The Nuclear Theory of the Atom 7
Quantum Theory of Spectra 10
Hydrogen Spectrum 12
The Pickering Lines 15
Other Spectra 18

ESSAY II

ON THE SERIES SPECTRA OF THE ELEMENTS

I. INTRODUCTION 20

II. GENERAL PRINCIPLES OF THE QUANTUM THEORY OF SPECTRA . 23

Hydrogen Spectrum 24
The Correspondence Principle 27
General Spectral Laws 29
Absorption and Excitation of Radiation 32

III. DEVELOPMENT OF THE QUANTUM THEORY OF SPECTRA . . 36

Effect of External Forces on the Hydrogen Spectrum . . 37
The Stark Effect 39
The Zeeman Effect
Central Perturbations .... ^ ... 42
44
Relativity Effect on Hydrogen Lines 46
Theory of Series Spectra 48
Correspondence Principle and Conservation of Angular Mo-
mentum 50
The Spectra of Helium and Lithium 54
Complex Structure of Series Lines 58

IV. CONCLUSION . 59
 CONTENTS

ESSAY III

THE STRUCTURE OF THE ATOM AND THE PHYSICAL

AND CHEMICAL PROPERTIES OF THE ELEMENTS
PAGE
I. PRELIMINARY 61
The Nuclear Atom 61
The Postulates of the Quantum Theory 62
Hydrogen Atom 63
Hydrogen Spectrum and X-ray Spectra
The Fine Structure of the Hydrogen Lines
Periodic Table
.... 65
67
69
Recent Atomic Models 74

II. SERIES SPECTRA AND THE CAPTURE OF ELECTRONS BY ATOMS . 75

Arc and Spark Spectra 76
Series Diagram 78
Correspondence Principle 81

III. FORMATION OF ATOMS AND THE PERIODIC TABLE ... 85

First Period. Hydrogen Helium 85
Second Period. Lithium Neon 89
Third Period. Sodium Argon 95
Fourth Period. Potassium Krypton 100
Fifth-Period. Rubidium Xenon 108
Sixth Period. Caesium Niton 109
Seventh Period Ill

Survey of the Periodic Table 113

IV. REORGANIZATION OF ATOMS AND X-RAY SPECTRA . . .116

Absorption and Emission of X-rays and Correspondence Prin-
ciple 117

X-ray Spectra and Atomic Structure 119

Classification of X-ray Spectra 121

CONCLUSION 125
 ESSAY I*
ON THE SPECTRUM OF HYDROGEN
Empirical spectral laws. Hydrogen possesses not only the
smallest atomic weight of all it also occupies a
the elements, but
peculiar position both with regard to its physical and its chemical
properties. One of the points where this becomes particularly ap-
parent is the hydrogen line spectrum.
The spectrum of hydrogen observed in an ordinary Geissler tube
consists of a series of lines, the strongest of which lies at the red
end of the spectrum, while the others extend out into the ultra
violet, the distance between the various lines, as well as their in-

tensities, constantly decreasing. In the ultra violet the series con-

verges to a limit.
Balmer, as we know, discovered (1885) that it was possible to
represent the wave lengths of these lines very accurately by the
simple law

where R
is a constant and n is a whole number. The wave
lengths
of the five strongest hydrogen lines, corresponding to n = 3, 4, 5, 6,
7, measured in air at ordinary pressure and temperature, and the

values of these wave lengths multiplied by f

j
-- are given in
3}

the following table:

3 6563-04 91153-3
4 4861-49 91152-9
5 4340-66 91153-9
6 4101-85 91152-2
7 3970-25 91153-7

The table shows that the product is nearly constant, while the devia-
tions are not greater than might be ascribed to experimental errors.
As you already know, Balmer's discovery of the law relating to
the hydrogen spectrum led to the discovery of laws applying to
the spectra of other elements. The most important work in this
* Address delivered before the
Physical Society in Copenhagen, Dec. 20, 1913.
B. 1
 ON THE SPECTRUM OF HYDROGEN

connection was done by Rydberg (1890) and Ritz (1908). Rydberg

pointed out that the spectra ofmany elements contain series of
lines whose wave lengths are given approximately by the formula

\_ A R
2 '
\n (n -f- a)'

where A and a are constants having different values for the various
series, while R
is a universal constant equal to the constant in the

spectrum of hydrogen. If the wave lengths are measured in vacuo

Rydberg calculated the value of R to be 109675. In the spectra of
many elements, as opposed to the simple spectrum of hydrogen, there
are several series of lines whose wave lengths are to a close approxima-
tion given by Rydberg's formula if different values are assigned to
the constants A and a. Rydberg showed, however, in his earliest
work, that certain relations existed between the constants in the
various series of the spectrum of one and the same element. These
relations were later very successfully generalized by Ritz through
the establishment of the "combination principle." According to
this principle, the wave lengths of the various lines in the spectrum
of an element may be expressed by the formula

(2)

In this formula n^ and n z are whole numbers, and F (n), F^ (n), ... l is

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

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

is different for the different functions. A particular spectral line \vill,
according to this principle, correspond to each combination of n x
and w 2 as well as to the functions lt 2
,
F F The establishment of
,
. . . .

this principle led therefore to the prediction of a great number of

lines which were not included in the spectral formulae previously

considered, and in a large number of cases the calculations were

found to be in close agreement with the experimental observations.
In the case of hydrogen Ritz assumed that formula (1) was a special
case of the general formula
 ON THE SPECTRUM OF HYDROGEN 3

and therefore predicted among other things a series of lines in the

infra red givenby the formula
1

In 1909 Paschen succeeded in observing the first two lines of this

series
corresponding to n
= 4 and n = 5.
The part played by hydrogen in the development of our
knowledge of the spectral laws is not solely due to its ordinary
simple spectrum, but it can also be traced in other less direct
ways. At a time when Rydberg's laws were still in want of
further confirmation Pickering (1897) found in the spectrum of a
star a series of lines whose wave lengths showed a very simple re-
lation to the ordinary hydrogen spectrum, since to a very close

approximation they could be expressed by the formula

1

Rydberg considered these lines to represent a new series of lines

in the spectrum of hydrogen, and predicted according to his theory
the existence of still another series of hydrogen lines the wave
lengths of which would be given by
1

By examining earlier observations it was actually found that a line

had been observed in the spectrum of certain stars which coincided
closely with the first line in this series (corresponding to n
= 2) ;

from analogy with other spectra it was also to be expected that this
would be the strongest line. This was regarded as a great triumph
for Rydberg's theory and tended to remove all doubt that the new

spectrum was actually due to hydrogen. Rydberg's view has there-

fore been generally accepted by physicists up to the present moment.

Recently however the question has been reopened and Fowler

(1912) has succeeded in observing the Pickering lines in ordinary
laboratory experiments. We shall return to this question again
later.

The discovery of these beautiful and simple laws concerning the

line spectra of the elements has naturally resulted in many attempts
at a theoretical explanation. Such attempts are very alluring
12
4 ON THE SPECTRUM OF HYDROGEN

because the simplicity of the spectral laws and the exceptional accu-
racy with which they apply appear to promise that the correct expla-
nation will be very simple and will give valuable information
about the properties of matter. I should like to consider some of
these theories somewhat more closely, several of which are extremely

interesting and have been developed with the greatest keenness

and ingenuity, but unfortunately space does not permit me to do
so here. I shall have to limit myself to the statement that not
one of the theories so far proposed appears to offer a satisfactory or
even a plausible way of explaining the laws of the line spectra.
Considering our deficient knowledge of the laws which determine
the processes inside atoms it is scarcely possible to give an explana-
tion of the kind attempted in these theories. The inadequacy of
our ordinary theoretical conceptions has become especially apparent
from the important results which have been obtained in recent years
from the theoretical and experimental study of the laws of tem-
perature radiation. You will therefore understand that I shall not
attempt to propose an explanation of the spectral laws; on the
contrary I shall try to indicate a way in which it appears possible
to bring the spectral laws into close connection with other pro-

perties of the elements, which appear to be equally inexplicable on

the basis of the present state of the science. In these considerations
I shall employ the results obtained from the study of temperature
radiation as well as the view of atomic structure which has been
reached by the study of the radioactive elements.

Laws of temperature radiation. I shall commence by men-

tioning the conclusions which have been drawn from experimental
and theoretical work on temperature radiation.
Let us consider an enclosure surrounded by bodies which are in
temperature equilibrium. In this space there will be a certain
amount of energy contained in the rays emitted by the surrounding
substances and crossing each other in every direction. By making
the assumption that the temperature equilibrium will not be dis-
turbed by the mutual radiation of the various bodies Kirchhoff
(1860) showed that the amount of energy per unit volume as well
as the distribution of this energy among the various wave lengths
is independent of the form and size of the space and of the nature
 ON THE SPECTRUM OF HYDROGEN 5

of the surrounding bodies and depends only on the temperature.

Kirchhoff's result has been confirmed by experiment, and the
amount of energy and its distribution among the various wave
lengths and the manner in which it depends on the tempe-
rature are now fairly well known from a great amount of experi-
mental work or, as it is usually expressed, we have a fairly
;

accurate experimental knowledge of the "laws of temperature

radiation."
Kirchhoff's considerations were only capable of predicting the
existence of a law of temperature radiation, and many physicists
have subsequently attempted to find a more thorough explanation
of the experimental results. You will perceive that the electro-

magnetic theory of light together with the electron theory suggests

a method of solving this problem. According to the electron theory
of matter a body consists of a system of electrons. By making
certain definite assumptions concerning the forces acting on the
electrons it is possible to calculate their motion and consequently
the energy radiated from the body per second in the form of
electromagnetic oscillations of various wave lengths. In a similar
manner the absorption of rays of a given wave length by a substance
can be determined by calculating the effect of electromagnetic
oscillations upon the motion of the electrons. Having investigated
the emission and absorption of a body at all temperatures, and for

rays of all wave lengths, it is possible, as Kirchhoff has shown, to

determine immediately the laws of temperature radiation. Since
the result is to be independent of the nature of the body we are
an agreement with experiment, even though
justified in expecting
very special assumptions are made about the forces acting upon
the electrons of the hypothetical substance. This naturally

simplifies the problem considerably, but it is nevertheless suffi-

ciently difficult and it is remarkable that it has been possible
to make any advance at all in this direction. As is well known
this has been done by Lorentz (1903). He calculated the
emissive as well as the absorptive power of a metal for long
wave lengths, using the same assumptions about the motions
of the electrons in the metal that Drude (1900) employed in
his calculation of the ratio of the electricaland thermal conduc-
tivities. Subsequently, by calculating the ratio of the emissive
6 ON THE SPECTRUM OF HYDROGEN

to the absorptive power, Lorentz really obtained an expression

for the law of temperature radiation which for long wave lengths

agrees remarkably well with experimental facts.

In spite of this
beautiful and promising result, it has nevertheless become apparent
that the electromagnetic theory is incapable of explaining the law
of temperature radiation. For, it is possible to show, that, if the
investigation is not confined to oscillations of long wave lengths,
as in Lorentz's work, but is also extended to oscillations corre-

sponding to small wave lengths, results are obtained which are

contrary to experiment. This is especially evident from Jeans'
investigations (1905) in which he employed a very interesting
method first proposed by Lord Rayleigh.
statistical
We
are therefore compelled to assume, that the classical electro-

dynamics does not agree with reality, or expressed more carefully,

that it can not be employed in calculating the absorption and
emission of radiation by atoms. Fortunately, the law of temperature
radiation has also successfully indicated the direction in which the

necessary changes in the electrodynamics are to be sought. Even

before the appearance of the papers by Lorentz and Jeans, Planck

(1900) had derived theoretically a formula for the black body radia-
tion which was in good agreement with the results of experiment.
Planck did not limit himself exclusively to the classical electro-
dynamics, but introduced the further assumption that a system of
oscillating electrical particles (elementary resonators) will neither
radiate nor absorb energy continuously, as required by the ordinary

electrodynamics, but on the contrary will radiate and absorb dis-

continuously. The energy contained within the system at any
moment is always equal to a whole multiple of the so-called
quantum of energy the magnitude of which is equal to hv, where
h is Planck's constant and v is the frequency of oscillation of the
system per second. In formal respects Planck's theory leaves much
to be desired in certain calculations the
;
ordinary electrodynamics
is used, while in others
assumptions distinctly at variance with it
are introduced without
any attempt being made to show that it
is possible to give a consistent explanation of the procedure used.
Planck's theory would
hardly have acquired general recognition
merely on the ground of its agreement with experiments on black
body radiation, but, as you know, the theory has also contributed
 ON THE SPECTRUM OF HYDROGEN 7

quite remarkably to the elucidation of many different physical

phenomena, such as specific heats, photoelectric effect, X-rays and
the absorption of heat rays by gases. These explanations involve
more than the qualitative assumption of a discontinuous trans-
formation of energy, for with the aid of Planck's constant h it
seems to be possible, at least approximately, to account for a great
number of phenomena about which nothing could be said previously.
Itis therefore hardly too early to express the opinion that, whatever
"
the final explanation will be, the discovery of " energy quanta
must be considered as one of the most important results arrived at
in physics,and must be taken into consideration in investigations
of the properties of atoms and particularly in connection with any

explanation of the spectral laws in which such phenomena as

the emission and absorption of electromagnetic radiation are
concerned.

The nuclear theory of the atom. We shall now consider the

second part of the foundation on which we shall build, namely the
conclusions arrived at from experiments with the rays emitted by
radioactive substances. I have previously here in the Physical

Society had the opportunity of speaking of the scattering of a rays

in passing through thin plates, and to mention how Rutherford
(1911) has proposed a theory for the structure of the atom in
order to explain the remarkable and unexpected results of these

experiments. I shall, therefore, only remind you that the charac-

teristic feature of Rutherford's theory is the assumption of the
existence of a positively charged nucleus inside the atom. number A
of electrons are supposed to revolve in closed orbits around the
nucleus, the number of these electrons being sufficient to neutralize
the positive charge of the nucleus. The dimensions of the nucleus
are supposed to be very small in comparison with the dimensions
of the orbits of the electrons, and almost the entire mass of the
atom is supposed to be concentrated in the nucleus.

According to Rutherford's calculation the positive charge of the

nucleus corresponds to a number of electrons equal to about half
the atomic weight. This number coincides approximately with the
number of the particular element in the periodic system and it is
therefore natural to assume that the number of electrons in the
8 ON THE SPECTRUM OF HYDROGEN

number. This hypothesis, which was

atom exactly equal to this
is

first stated by van den Broek (1912), opens

the possibility of

a of the periodic system. This as-

obtaining simple explanation
on the elements
sumption is strongly confirmed by experiments
of small atomic weight. In the first place, it is evident that ac-
the a particle is the same as the
cording to Rutherford's theory
nucleus of a helium atom. Since the a particle has a double positive

charge it follows immediately that a neutral helium atom contains

two electrons. Further the concordant results obtained from cal-
culations based on experiments as different as the diffuse scatter-
in velocity of a rays in passing
ing of X-rays and the decrease
through matter render the conclusion extremely likely that a
This agrees most
hydrogen atom contains only a single electron.
beautifully with the fact that J. J. Thomson in his well-known
has never observed a
experiments on rays of positive electricity
hydrogen atom with more than a single positive charge, while all
other elements investigated may have several charges.
Let us now assume that a hydrogen atom simply consists of an
electron revolving around a nucleus of equal and opposite charge,
and of a mass which is very large in comparison with that of the
electron. It is evident that this assumption may explain the peculiar
position already referred to which hydrogen occupies among the
elements, but it appears at the outset completely hopeless to attempt
to explain anything at all of the special properties of hydrogen,
line spectrum, on the basis of considerations relating
still less its

to such a simple system.

Let us assume for the sake of brevity that the mass of the nucleus
is
infinitely large in proportion to that of the electron, and that the
velocity of the electron is very small in comparison with that of
light. If we now temporarily disregard the energy radiation, which,

according to the ordinary electrodynamics, will accompany the ac-

celerated motion of the electron, the latter in accordance with

Kepler's first law will describe an ellipse with the nucleus in one
of the foci.
Denoting the frequency of revolution o>, and the
by
major axis of the ellipse by 2a we find that

2TF3 P*
 ON THE SPECTRUM OF HYDROGEN 9

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

the work which must be added to the system in order to remove
the electron to an infinite distance from the nucleus.
These expressions are extremely simple and they show that the
magnitude of the frequency of revolution as well as the length of
the major axis depend only on W, and are independent of the

excentricity of the orbit. By varying W

we may obtain all possible
values for &> and 2a. This condition shows, however, that it is not

possible to employ the above formulae directly in calculating the

orbit of the electron in a hydrogen atom. For this it will be necessary
to assume that the orbit of the electron can not take on all values,
and in any event, the line spectrum clearly indicates that the
oscillations of the electron cannot vary continuously between wide
limits. The impossibility of making any progress with a simple

system like the one considered here might have been foretold from
a consideration of the dimensions involved for with the aid of e
;

and m alone impossible to obtain a quantity which can be

it is

interpreted as a diameter of an atom or as a frequency.

If we attempt to account for the radiation of energy in the manner

required by the ordinary electrodynamics it will only make matters

worse. As a result of the radiation of energy W
would continually
increase, and the above expressions show that at the same time
(4)
the frequency of revolution of the system would increase, and the
dimensions of the orbit decrease. This process would not stop until
the particles had approached so closely to one another that they no
longer attracted each other. The quantity of energy which would
be radiated away before this happened would be very great. If we
were to treat these particles as geometrical points this energy would
be infinitely great, and with the dimensions of the electrons as
calculated from their mass (about 10~ 13 cm.), and of the nucleus as
calculated by Rutherford (about 10~ 12 cm.), this energy would be

many times greater than the energy changes with which we are
familiar in ordinary atomic processes.
It can be seen that it is impossible to employ Rutherford's atomic
model so long as we confine ourselves exclusively to the ordinary
electrodynamics. But this is nothing more than might have been
expected. As I have mentioned we may consider it to be an
established fact that it is impossible to obtain a satisfactory
JO ON THE SPECTRUM OF HYDROGEN

on temperature radiation with the

explanation of the experiments
aid of electrodynamics, no matter what atomic model be em-

ployed.
The fact that the deficiencies of the atomic model we are
so plainly is therefore perhaps no serious
considering stand out
drawback; even the defects of other atomic models are
though
much better concealed they must nevertheless be present and will

be just as serious.

Quantum theory of spectra. Let us now try to overcome these

difficulties by applying Planck's theory to the problem.
It is readily seen that there
can be no question of a direct appli-
cation of Planck's theory. This theory is concerned with the emission
and absorption of energy in a system of electrical particles, which
with a given frequency per second, dependent only on the
oscillate
nature of the system and independent of the amount of energy
contained in the system. In a system consisting of an electron and
a nucleus the period of oscillation corresponds to the period of
revolution of the electron. But the formula (4) for <w shows that the
frequency of revolution depends upon W, i.e. on the energy of the
system. Still the fact that we can not immediately apply Planck's
theory to our problem is not as serious as it might seem to be, for
in assuming Planck's theory we have manifestly acknowledged the
inadequacy of the ordinary electrodynamics and have definitely
parted with the coherent group of ideas on which the latter theory
is based. In fact in
taking such a step we can not expect that all
cases of disagreement between the theoretical conceptions hitherto

employed and experiment will be removed by the use of Planck's

assumption regarding the quantum of the energy momentarily
present in an oscillating system. We stand here almost entirely on
virgin ground, and upon introducing new assumptions we need only
take care not to get into contradiction with
experiment. Time will
have to show to what extent this can be avoided but the safest ;

way is, of course, to make as few assumptions as possible.

With this in mind let us first examine the
experiments on
temperature radiation. The subject of direct observation is the
distribution of radiant wave
energy over oscillations of the various
Even though we may assume that this
lengths. energy comes from
systems of oscillating particles, we know little or nothing about
 ON THE SPECTRUM OF HYDROGEN 11

these systems. No one has ever seen a Planck's resonator, nor

indeed even measured its frequency of oscillation we can observe
;

only the period of oscillation of the radiation which is emitted. It

is therefore very convenient that it is possible to show that to

obtain the laws of temperature radiation it is not necessary to

make any assumptions about the systems which emit the radiation
except that the amount of energy emitted each time shall be equal
to hv, where h is Planck's constant and v is the frequency of the
radiation. Indeed, it possible to derive Planck's law of radiation
is

from this assumption alone, as shown by Debye, who employed a

method which is a combination of that of Planck and of Jeans.
Before considering any further the nature of the oscillating systems
letus see whether it is possible to bring this assumption about the
emission of radiation into agreement with the spectral laws.
If the spectrum of some element contains a spectral line corre-

sponding to the frequency v it will be assumed that one of the

atoms of the element (or some other elementary system) can emit
an amount of energy hv. Denoting, the energy of the atom before
and after the emission of the radiation by E l and E a we have

(5)

During the emission of the radiation the system may be regarded

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

for these states, we them "stationary" states, simply

shall call

indicating thereby that they form some kind of waiting places

between which occurs the emission of the energy corresponding to
the various spectral lines. As previously mentioned the spectrum
of an element consists of a series of lines whose wave lengths may
be expressed by the formula (2). By comparing this expression

with the relation given above it is seen that since v = - where

,
c
A.

is the velocity of light each of the spectral lines may be regarded

as being emitted by the transition of a system between two stationary
states in which the energy apart from an additive arbitrary
constant is
given by chFr (n ) and chFs (n 2 ) respectively. Using
a

this interpretation the combination principle asserts that a series

of stationary states exists for the given system, and that it can
12 ON THE SPECTRUM OF HYDROGEN

pass from one to any other of these states with the emission of
a monochromatic radiation. We see, therefore, that with a simple
extension of our first assumption it is possible to give a formal
explanation of the most general law of line spectra.

Hydrogen spectrum. This result encourages us to make an

attempt to obtain a clear conception of the stationary states which
have so far only been regarded as formal. With this end in view,
we naturally turn to the spectrum of hydrogen. The formula
applying to this spectrum is
given by the expression

i^R_R
\ nf nf
According to our assumption this spectrum is produced by tran-
sitions between a series of stationary states of a system, concerning
which we can for the present only say that the energy of the system
in the nth state, apart from an additive constant, is given by
-- ri*
. Let us now try
J to find a connection between this and the

model of the hydrogen atom. We assume that in the calculation

of the frequency of revolution of the electron in the stationary states
of the atom it will be possible to employ the above formula for .

It is quite natural to make this assumption ; since, in trying to

form a reasonable conception of the stationary states, there is, for
the present atleast, no other means available besides the ordinary
mechanics.

Corresponding to the nth stationary state in formula (4) for to,

let us by way of experiment put W= ^ . This gives us

The
radiation of light
corresponding to a particular spectral line
is
according to our assumption emitted by a transition between
two stationary states,
corresponding to two different frequencies of
revolution, and we are not justified in
expecting any simple re-
lation between these
frequencies of revolution of the electron and
the frequency of the emitted radiation. You
understand, of course,
that I am by no means
trying to give what might ordinarily be
described as an explanation;
nothing has been said here about
 ON THE SPECTRUM OF HYDROGEN 13

how why the radiation is emitted. On one point, however, we

or

may expect a connection with the ordinary conceptions namely. ;

that it will be possible to calculate the emission of slow electro-

magnetic oscillations on the basis of the classical electrodynamics.

This assumption is very strongly supported by the result of
Lorentz's calculations which have already been described. From
the formula for a> it is seen that the frequency of revolution de-

creases as n increases, and that the expression approaches the

n+i
value 1.

According to what has been said above, the frequency of the

radiation corresponding to the transition between the (n + l)th
and the nth stationary state is given by

v = Re I .
*
(n +
If n is very large this expression is approximately equal to
v = 2Rc(n 3
.

In order to obtain a connection with the ordinary electrodynamics

let us now place this frequency equal to the frequency of revolu-

tion, that is
w n = 2Rc/n 3 .

Introducing this value of &> in (6) we

see that n disappears from
the equation, and further that the equation will be satisfied only if

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

before, equal to 109675. By introducing the most recent values
for e, m
and h the expression on the right-hand side of the equa-
tion becomes equal to 1'09 . 10*. The agreement is as good as
could be expected, considering the uncertainty in the experimental
determination of the constants e, m
and h. The agreement between
our calculations and the classical electrodynamics is, therefore,
fully as good as we are justified in expecting.
We
can not expect to obtain a corresponding explanation of the
frequency values of the other stationary states. Certain simple
formal relations apply, however, to all the stationary ^tates. By
introducing the expression, which has been found for R, we

get for the wth state Wn = %nha) n . This equation is entirely

14 ON THE SPECTRUM OF HYDROGEN
the energy of a
analogous to Planck's assumption concerning
resonator. W
in our system is readily shown to be equal to the
of the electron during a
average value of the kinetic energy
single revolution. The energy of a resonator was shown by Planck
to be always equal to nhv. Further the average
you may remember
value of the kinetic energy of Planck's resonator is equal to its
value of the kinetic energy
potentialenergy, so that the average
of the resonator, according to Planck, is equal to %nhco. This

analogy suggests another

manner of presenting the theory, and it
was just in this way that I was originally led into these con-
siderations. When we consider how differently the equation is

employed here and in Planck's theory

it appears to me misleading
to use this analogy as a foundation, and in the account I have
as much as possible from it.
given I have tried to free myself
Let us continue with the elucidation of the calculations, and in
the expression for 2a introduce the value of If which corresponds
to the nth stationary state.This gives us

2a =w 2
.
-^3 = n
ckR
2
.
^,
22 =
t
w2 . 11 . 10~ 8 . . .
.(8)

It is seen that for small values of n, we obtain values for the

major axis of the orbit of the electron which are of the same
order of magnitude as the values of the diameters of the atoms
calculated from the kinetic theory of gases. For large values of
n, 2a becomes very large in proportion to the calculated dimensions
of the atoms. This, however, does not necessarily disagree with
experiment. Under ordinary circumstances a hydrogen atom will
probably exist only in the state corresponding to n
= 1. For this
state W
will have its greatest value and, consequently, the atom
will have emitted the largest amount of energy possible this will ;

therefore represent the most stable state of the atom from which
the system can not be transferred except by adding energy to it
from without. The large values for 2a corresponding to large n need
not, therefore, be contrary to experiment ; indeed, we may in these

large values seek an explanation of the fact, that in the laboratory

it has hitherto not been
possible to observe the hydrogen lines
corresponding to large values of n in Balmer's formula, while they
have been observed in the spectra of certain stars. In order that
the large orbits of the electrons
may not be disturbed by electrical