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The Project Gutenberg eBook of On the quantum
theory of radiation and the structure of the atom
This ebook is for the use of anyone anywhere in the United States
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Title: On the quantum theory of radiation and the structure of the

atom

Author: Niels Bohr

Release date: March 2, 2024 [eBook #73087]

Language: English

Original publication: London: The London, Edinburgh, and Dublin

Philosophical Magazine and Journal of Science, 1915

Credits: Laura Natal Rodrigues (Images generously made available

by The Internet Archive.)

*** START OF THE PROJECT GUTENBERG EBOOK ON THE

QUANTUM THEORY OF RADIATION AND THE STRUCTURE OF
THE ATOM ***
 THE LONDON, EDINBURGH, AND DUBLIN
PHILOSOPHICAL MAGAZINE
and
JOURNAL OF SCIENCE.

VOL. XXX—SIXTH SERIES.

JULY-DECEMBER 1915.

XLII. On the Quantum Theory of

Radiation and the Structure of
the Atom.

By N. BOHR,

Dr. phil. Copenhagen;

p.t. Reader in Mathematical Physics at the University
of Manchester[1].
 CONTENTS
§ 1. General assumptions.
§ 2. Spectra emitted from systems containing only one electron.
§ 3. Spectra emitted from systems containing more than one
electron.
§ 4. The high frequency spectra of the elements.

IN a series of papers in this periodical[2] the present writer has

attempted to give the outlines of a theory of the constitution of atoms
and molecules by help of a certain application of the Quantum theory
of radiation to the theory of the nucleus atom. As the theory has
been made a subject of criticism, and as experimental evidence of
importance bearing on these questions has been obtained in the
meantime, an attempt will be made in this paper to consider some
points more closely.
 § 1. General assumptions.
According to the theory proposed by Sir Ernest Rutherford, in
order to account for the phenomena of scattering of -rays, the atom
consists of a central positively charged nucleus surrounded by a
cluster of electrons. The nucleus is the seat of the essential part of
the mass of the atom, and has linear dimensions exceedingly small
compared with the distances apart of the electrons in the
surrounding cluster. From the results of experiments on scattering of
alpha rays, Rutherford concluded that the charge on the nucleus
corresponds to a number of electrons per atom approximately equal
to half the atomic weight. Concordant evidence from a large number
of very different phenomena has led to the more definite assumption
that the number of electrons per atom is exactly equal to the atomic
number, i.e., the number of the corresponding element in the
periodic table. This view was first proposed by van den Broek[3].
While the nucleus theory has been of great utility in explaining many
important properties of the atom[4], on the other hand it is evident
that it is impossible by its aid to explain many other fundamental
properties if we base our considerations on the ordinary
electrodynamical theory; but this can hardly be considered as a valid
objection at the present time. It does not seem that there is any
escape from the conclusion that it is impossible to account for the
phenomena of temperature radiation on ordinary electrodynamics,
and that the modification to be introduced in this theory must be
essentially equivalent with the assumptions first used by Planck in
the deduction of his radiation formula[5]. These assumptions are
known as the Quantum theory. In my previous paper it was
attempted to apply the main principles of this theory by introducing
the following general assumptions:—
A. An atomic system possesses a number of states in which no
emission of energy radiation takes place, even if the particles
 are in motion relative to each other, and such an emission is to
be expected on ordinary electrodynamics. The states are
denoted as the “stationary” states of the system under
consideration.
B. Any emission or absorption of energy radiation will correspond to
the transition between two stationary states. The radiation
emitted during such a transition is homogeneous and the
frequency is determined by the relation

where is Planck’s constant and , and , are the energies

of the system in the two stationary states.
C. That the dynamical equilibrium of the systems in the stationary
states is governed by the ordinary laws of mechanics, while
these laws do not hold for the transition from one state to
another.
D. That the various possible stationary states of a system consisting
of an electron rotating round a positive nucleus are determined
by the relation

where is the mean value of the kinetic energy of the system,

the frequency of rotation, and a whole number.
It will be seen that these assumptions are closely analogous to
those originally used by Planck about the emission of radiation in
quanta, and about the relation between the frequency of an atomic
resonator (of constant frequency) and its energy. It can be shown
that, for any system containing one electron rotating in a closed orbit,
the assumption C and the relation (2) will secure a connexion
between the frequency calculated by (1) and that to be expected
from ordinary electrodynamics, in the limit where the difference
between the frequency of the rotation of the electron in successive
stationary states is very small compared with the absolute value of
the frequency (see IV. p. 5). On the nucleus theory this occurs in the
region of very slow vibrations. If the orbit of the electron is circular,
the assumption D is equivalent to the condition that the angular
momentum of the system in the stationary states is an integral
multiple of . The possible importance of the angular momentum
in the discussion of atomic systems in relation to Planck’s theory was
first pointed out by J. W. Nicholson[6].
In paper I. it was shown that the above assumptions lead to an
interpretation of the Balmer formula for the hydrogen spectrum, and
to a determination of the Rydberg constant which was in close
agreement with the measurements. In these considerations it is not
necessary to make any assumption about the degree of excentricity
of the orbit of the electron, and we shall see in the next section that it
cannot be assumed that the orbit is always circular.
So far we have considered systems which contain only one
electron, but the general validity of the assumptions A and B seems
strongly supported by the fact that they offer a simple interpretation
of the general principle of combination of spectral lines (see IV. p. 2).
This principle was originally discovered by Ritz to hold for the
ordinary series spectra of the elements. It has recently acquired
increased interest by Fowler’s work on the series spectra of
enhanced lines emitted from many elements when subject to a
powerful electric discharge. Fowler showed that the principle of
combination holds for these spectra although the laws governing the
numerical relation between the lines at an important point (see
section 3) differed from those of the ordinary series spectra. There is
also, as we shall see in section 4, some indication that the principle
holds for the high frequency spectra revealed by interference in
crystals. In this connexion it may also be remarked that the
assumption A recently has obtained direct support by experiments of
A. Einstein and J. W. de Haas[7], who have succeeded in detecting
and measuring a rotational mechanical effect produced when an iron
bar is magnetized. Their results agree very closely with those to be
expected on the assumption that the magnetism of iron is due to
rotating electrons, and as pointed out by Einstein and Haas, these
experiments therefore indicate very strongly that electrons can rotate
in atoms without emission of energy radiation.
When we try to apply assumptions, analogous with C and D, to
systems containing more than one electron, we meet with difficulties,
since in this case the application of ordinary mechanics in general
does not lead to periodic orbits. An exception to this, however,
occurs if the electrons are arranged in rings and rotate in circular
orbits, and from simple considerations of analogy the following
assumption was proposed (see I. p. 24).
E. In any atomic or molecular system consisting of positive nuclei
and electrons in which the nuclei are at rest relative to each
other, and the electrons move in circular orbits, the angular
momentum of each electron round the centre of its orbit will be
equal to in the “normal” state of the system, i.e. the state in
which the total energy is a minimum.
It was shown that in a number of different cases this assumption
led to results in approximate agreement with experimental facts. In
general, no stable configuration in which the electrons rotate in
circular orbits can exist if the problem of stability is discussed on
ordinary mechanics. This is no objection, however, since it is
assumed already that the mechanics do not hold for the transition
between two stationary states. Simple considerations led to the
following condition of stability.
F. A configuration satisfying the condition E is stable if the total
energy of the system is less than in any neighbouring
configuration satisfying the same condition of angular
momentum of the electrons.
As already mentioned, the foundation for the hypothesis E was
sought in analogy with the simple system consisting of one electron
and one nucleus. Additional support, however, was obtained from a
closer consideration of the formation of the systems. It was shown
how simple processes could be imagined by which the confluence of
different rings of electrons could be effected without any change in
the angular momentum of the electrons, if the angular momentum of
each electron before the process was the same. Such
considerations led to a theory of formation of molecules.
It must be emphasized that only in the case of circular orbits has
the angular momentum any connexion with the principles of the
Quantum theory. If, therefore, the application of ordinary mechanics
to the stationary states of the system does not lead to strictly circular
orbits, the assumption E cannot be applied. This case occurs if we
consider configurations in which the electrons are arranged in
different rings which do not rotate with the same frequency. Such
configurations, however, are apparently necessary in order to explain
many characteristic properties of the atoms. In my previous papers
an attempt was made in certain cases to overcome this difficulty by
assuming, that if a very small alteration of the forces would make
circular orbits possible on ordinary mechanics, the configuration and
energy of the actual system would only differ very little from that
calculated for the altered system. It will be seen that this assumption
is most intimately connected with the hypothesis F on the stability of
the configurations. Such considerations were used to explain the
general appearance of the Rydberg constant in the spectra of the
elements, and were also applied in discussing possible
configurations of the electrons in the atoms suggested by the
observed chemical properties. These calculations have been
criticised by Nicholson[8], who has attempted to show that the
configurations chosen for the electrons in the atoms are inconsistent
with the main principles of the theory, and has also attempted to
prove the impossibility of accounting for other spectra by help of
assumptions similar to those used in the interpretation of the
hydrogen spectrum.
Although I am quite ready to admit that these points involve great
and unsolved difficulties, I am unable to agree with Nicholson’s
conclusions. In the first place, his calculations rest upon a particular
application to non-circular orbits of the principle of constancy of
angular momentum for each electron, which it does not seem
possible to justify either on the Quantum theory or on the ordinary
mechanics, and which has no direct connexion with the assumptions
used in my papers. It has not been proved that the configurations
proposed are inconsistent with the assumption C. But even if it were
possible to prove that the unrestricted use of ordinary mechanics to
the stationary states is inconsistent with the configurations of the
electrons, apparently necessary to explain the observed properties
of the elements, this would not constitute a serious objection to the
deductions in my papers. It must be remarked that all the
applications of ordinary mechanics are essentially connected with
the assumption of periodic orbits. As far as the applications are
concerned, the first part of the assumption C might just as well have
been given the following more cautious form:—
“The relation between the frequency and energy of the particles
in the stationary states can be determined by means of the ordinary
laws of mechanics if these laws lead to periodic orbits.”
The possible necessity for an alteration of this kind in assumption
C may perhaps not seem unlikely when it is remembered that the
laws of mechanics are only known to hold for certain mean values of
the motion of the electrons. In this connexion it should also be
remarked that when considering periodic orbits only mean values are
essential (comp. I. p. 7). The preliminary and tentative character of
the formulation of the general assumptions cannot be too strongly
emphasized, and admittedly they are made to suit certain simple
applications. For example, it has been already shown in paper IV.
that the assumption B needs modification in order to account for the
effect of a magnetic field on spectral lines. In the following sections
some of the recent experimental evidence on line spectra and
characteristic Röntgen rays will be considered, and I shall endeavour
to show that it seems to give strong support to the main principles of
the theory.
 § 2. Spectra emitted from systems
containing only one electron.
In the former papers it was shown that the general assumptions
led to the following formula for the spectrum emitted by an electron
rotating round a positive nucleus

, , , are the electric charges and the masses of the

nucleus and the electron respectively. The frequency of rotation and
the major axis of the relative orbit of the particles in the stationary
states are given by

The energy necessary to remove the electron to infinite distance from

the nucleus is

This expression is also equal to the mean value of the kinetic energy
of the system. Since is equal to the total energy of the
system we get from (4) and (5)
If we compare (6) with the relation (1), we see that the connexion with
ordinary mechanics in the region of slow vibration, mentioned in the
former section, is satisfied.
Putting in (3) we get the ordinary series spectrum of
hydrogen. Putting we get a spectrum which, on the theory,
should be expected to be emitted by an electron rotating round a
helium nucleus. The formula is found very closely to represent some
series of lines observed by Fowler[9] and Evans[10]. These series
correspond to and [11]. The theoretical value for the
ratio between the second factor in (3) for this spectrum and for the
hydrogen spectrum is 1.000409; the value calculated from Fowler’s
measurements is 1.000408[12]. Some of the lines under consideration
have been observed earlier in star spectra, and have been ascribed
to hydrogen not only on account of the close numerical relation with
the lines of the Balmer series, but also on account of the fact that the
lines observed, together with the lines of the Balmer series,
constitutes a spectrum which shows a marked analogy with the
spectra of the alkali metals. This analogy, however, has been
completely disturbed by Fowler’s and Evans’ observations, that the
two new series contain twice as many lines as is to be expected on
this analogy. In addition, Evans has succeeded in obtaining the lines
in such pure helium that no trace of the ordinary hydrogen lines could
be observed[13]. The great difference between the conditions for the
production of the Balmer series and the series under consideration is
also brought out very strikingly by some recent experiments of
Rau[14] on the minimum voltage necessary for the production of
spectral lines. While about 13 volts was sufficient to excite the lines of
the Balmer series, about 80 volts was found necessary to excite the
other series. These values agree closely with the values calculated
from the assumption E for the energies necessary to remove the
electron from the hydrogen atom and to remove both electrons from
the helium atom, viz. 13.6 and 81.3 volts respectively. It has recently
been argued[15] that the lines are not so sharp as should be expected
from the atomic weight of helium on Lord Rayleigh’s theory of the
width of spectral lines. This might, however, be explained by the fact
that the systems emitting the spectrum, in contrast to those emitting
the hydrogen spectrum, are supposed to carry an excess positive
charge, and therefore must be expected to acquire great velocities in
the electric field in the discharge-tube.
In paper IV. an attempt was made on the basis of the present
theory to explain the characteristic effect of an electric field on the
hydrogen spectrum recently discovered by Stark. This author
observed that if luminous hydrogen is placed in an intense electric
field, each of the lines of the Balmer series is split up into a number of
homogeneous components. These components are situated
symmetrically with regard to the original lines, and their distance
apart is proportional to the intensity of the external electric field. By
spectroscopic observation in a direction perpendicular to the field, the
components are linearly polarized, some parallel and some
perpendicular to the field. Further experiments have shown that the
phenomenon is even more complex than was at first expected. By
applying greater dispersion, the number of components observed has
been greatly increased, and the numbers as well as the intensities of
the components are found to vary in a complex manner from line to
line[16]. Although the present development of the theory does not
allow us to account in detail for the observations, it seems that the
considerations in paper IV. offer a simple interpretation of several
characteristic features of the phenomenon.
The calculation can be made considerably simpler than in the
former paper by an application of Hamilton’s principle. Consider a
particle moving in a closed orbit in a stationary field. Let be the
frequency of revolution, the mean value of the kinetic energy
during the revolution, and the mean value of the sum of the kinetic
energy and the potential energy of the particle relative to the
stationary field. We have then for a small arbitrary variation of the
orbit

This equation was used in paper IV. to prove the equivalence of the
formulæ (2) and (6) for any system governed by ordinary mechanics.
The equation (7) further shows that if the relations (2) and (6) hold for
a system of orbits, they will hold also for any small variation of these
orbits for which the value of is unaltered. If a hydrogen atom in
one of its stationary states is placed in an external electric field and
the electron rotates in a closed orbit, we shall therefore expect that
is not altered by the introduction of the atom in the field, and that
the only variation of the total energy of the system will be due to the
variation of the mean value of the potential energy relative to the
external field.
In the former paper it was pointed out that the orbit of the electron
will be deformed by the external field. This deformation will in course
of time be considerable even if the external electric force is very small
compared with the force of attraction between the particles. The orbit
of the electron may at any moment be considered as an ellipse with
the nucleus in the focus, and the length of the major axis will
approximately remain constant, but the effect of the field will consist
in a gradual variation of the direction of the major axis as well as the
excentricity of the orbit. A detailed investigation of the very
complicated motion of the electron was not attempted, but it was
simply pointed out that the problem allows of two stationary orbits of
the electron, and that these may be taken as representing two
possible stationary states. In these orbits the excentricity is equal to
1, and the major axis parallel to the external force; the orbits simply
consisting of a straight line through the nucleus parallel to the axis of
the field, one on each side of it. It can very simply be shown that the
mean value of the potential energy relative to the field for these
rectilinear orbits is equal to , where is the external electric
force and the major axis of the orbit, and the two signs correspond
to orbits in which the direction of the major axis from the nucleus is
the same or opposite to that of the electric force respectively. Using
the formulæ (4) and (5) and neglecting the mass of the electron
compared with that of the nucleus, we get, therefore, for the energy of
the system in the two states
respectively. This expression is the same as that deduced in paper IV.
by an application of (6) to the expressions for the energy and
frequency of the system. Applying the relation (1) and using the same
arguments as in paper IV. p. 10, we are therefore led to expect that
the hydrogen spectrum in an electric field will contain two
components polarized parallel to the field and of a frequency given by

The table below contains Stark’s recent measurements of the

frequency difference between the two strong outer components
polarized parallel to the field for the five first lines in the Balmer
series[17]. The first column gives the values for the numbers and
. The second and fourth columns give the frequency difference
corresponding to a field of 28500 and 74000 volts per cm.
respectively. The third and fifth columns give the values of

where should be a constant for all the lines and equal to unity.
28500 volts. per cm. 74000 volts. per cm.

2 3 0.46 0.83
2 4 1.04 0.79 2.86 0.83
2 5 2.06 0.89 5.41 0.90
2 6 3.16 0.90 7.81 0.85
2 7 4.47 0.90
Considering the difficulties of accurate measurement of the
quantities involved, it will be seen that the agreement with regard to
the variation of the frequency differences from line to line is very
good. The fact that all the observed values are a little smaller than the
calculated may be due to a slight over-estimate of the intensity of the
fields used in the experiments (see Stark, loc. cit. pp. 38 and 118).
Besides the two strong outer components polarized parallel to the
field, Stark’s experiments have revealed a large number of inner
weaker components polarized in the same way, and also a number of
components polarized perpendicular to the field. This complexity of
the phenomenon, however, cannot be considered as inconsistent with
the theory. The above simple calculations deal only with the two
extreme cases, and we may expect to find a number of stationary
states corresponding to orbits of smaller excentricity. In a discussion
of such non-periodic orbits, however, the general principles applied
are no longer sufficient guidance.
Apart from the agreement with the calculations, Stark’s
experiments seem to give strong support to the interpretation of the
origin of the two outer components. It was found that the two outer
components have not always equal intensities; when the spectrum is
produced by positive rays, it was found that the component of highest
frequency is the stronger if the rays travel against the electric field,
while if it travels in the direction of the field the component of smallest
frequency is the stronger (loc. cit. p. 40). This indicates that the
components are produced independently of each other—a result to
be expected if they correspond to quite different orbits of the electron.
That the orbit of the electron in general need not be circular is also
very strongly indicated by the observation that the hydrogen lines
emitted from positive rays under certain conditions are partly
polarized without the presence of a strong external field (loc. cit. p.
12). This polarization, as well as the observed intensity differences of
the two components, would be explained if we can assume that for
some reason, when the atom is in rapid motion, there is a greater
probability for the orbit of the electron to lie behind the nucleus rather
than in front of it.
 § 3. Spectra emitted from systems
containing more than one electron.
According to Rydberg and Ritz, the frequency of the lines in the
ordinary spectrum of an element is given by

where and are whole numbers and , , ...... are a series of

functions of which can be expressed by

where is a universal constant and a function which for large

values of approaches unity. The complete spectrum is obtained by
combining the numbers and , as well as the functions ,
...... in every possible way.
On the present theory, this indicates that the system which emits
the spectrum possesses a number of series of stationary states for
which the energy in the th state in the th series is given by (see IV.
p. 6)

where is an arbitrary constant, the same for the whole system of

stationary states. The first factor in the second term is equal to the
expression (5) if .
In the present state of the theory it is not possible to account in
detail for the formula (13), but it was pointed out in my previous
papers that a simple interpretation can be given of the fact that in
every series approaches unity for large values of . It was
assumed that in the stationary states corresponding to such values
of , one of the electrons in the atom moves at a distance from the
nucleus large compared with the distance of the other electrons. If
the atom is neutral, the outer electron will be subject to very nearly
the same forces as the electron in the hydrogen atom, and the
formula (13) indicates the presence of a number of series of
stationary states of the atom in which the configuration of the inner
electrons is very nearly the same for all states in one series, while
the configuration of the outer electron changes from state to state in
the series approximately in the same way as the electron in the
hydrogen atom. From the considerations in the former sections it will
therefore appear that the frequency calculated from the relations (1)
and (13) for the radiation emitted during the transition between
successive stationary states within each series will approach that to
be expected on ordinary electrodynamics in the region of slow
vibrations[18].
From (13) it follows that for high values of the configuration of
the inner electrons possesses the same energy in all the series of
stationary states corresponding to the same spectrum (11). The
different series of stationary states must therefore correspond to
different types of orbits of the outer electron, involving different
relations between energy and frequency. In order to fix our ideas, let
us for a moment consider the helium atom. This atom contains only
two electrons, and in the previous papers it was assumed that in the
normal state of the atom the electrons rotate in a circular ring round
a nucleus. Now the helium spectrum contains two complete systems
of series given by formulæ of the type (11) and the measurements of
Rau mentioned below indicate that the configuration of the inner
electron in the two corresponding systems of stationary states
possesses the same energy. A simple assumption is therefore that in
one of the two systems the orbit of the electron is circular and in the
other very flat. For high values of the inner electron in the two
configurations will act on the outer electron very nearly as a ring of
uniformly distributed charge with the nucleus in the centre or as a
line charge extending from the nucleus, respectively. In both cases