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[42]
Central Perturbations[44]
Relativity Effect on Hydrogen Lines[46]
Theory of Series Spectra[48]
Correspondence Principle and Conservation of Angular Momentum[50]
The Spectra of Helium and Lithium[54]
Complex Structure of Series Lines[58]
IV.CONCLUSION[59]
ESSAY III
THE STRUCTURE OF THE ATOM AND THE PHYSICAL AND CHEMICAL PROPERTIES OF THE ELEMENTS
I.PRELIMINARY[61]
The Nuclear Atom[61]
The Postulates of the Quantum Theory[62]
Hydrogen Atom[63]
Hydrogen Spectrum and X-ray Spectra[65]
The Fine Structure of the Hydrogen Lines[67]
Periodic Table[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[111]
Survey of the Periodic Table[113]
IV.REORGANIZATION OF ATOMS AND X-RAY SPECTRA[116]
Absorption and Emission of X-rays and Correspondence Principle[117]
X-ray Spectra and Atomic Structure[119]
Classification of X-ray Spectra[121]
Conclusion[125]

ESSAY I
ON THE SPECTRUM OF HYDROGEN[1]

Empirical spectral laws. Hydrogen possesses not only the smallest atomic weight of all the elements, but it also occupies a peculiar position both with regard to its physical and its chemical properties. One of the points where this becomes particularly apparent 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 intensities, constantly decreasing. In the ultra-violet the series converges 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

is a constant and

is a whole number. The wave lengths of the five strongest hydrogen lines, corresponding to

, measured in air at ordinary pressure and temperature, and the values of these wave lengths multiplied by

are given in the following table:

·
36563.04 91153.3
44861.49 91152.9
54340.66 91153.9
64101.85 91152.2
73970.25 91153.7

The table shows that the product is nearly constant, while the deviations 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 connection was done by Rydberg (1890) and Ritz (1908). Rydberg pointed out that the spectra of many elements contain series of lines whose wave lengths are given approximately by the formula

where

and

are constants having different values for the various series, while

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

to be

. 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 approximation given by Rydberg's formula if different values are assigned to the constants

and

. 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

In this formula

and

are whole numbers, and

is a series of functions of

, which may be written approximately

where

is Rydberg's universal constant and

is a constant which is different for the different functions. A particular spectral line will, according to this principle, correspond to each combination of

, as well as to the functions

. 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

and therefore predicted among other things a series of lines in the infra-red given by the formula

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

.

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 relation to the ordinary hydrogen spectrum, since to a very close approximation they could be expressed by the formula

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

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

); 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 therefore 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 because the simplicity of the spectral laws and the exceptional accuracy with which they apply appear to promise that the correct explanation 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 explanation 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 temperature 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 properties 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 mentioning 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 disturbed 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 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 temperature are now fairly well known from a great amount of experimental 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 electromagnetic 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 justified in expecting an agreement with experiment, even though 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 sufficiently 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 electrical and thermal conductivities. Subsequently, by calculating the ratio of the emissive 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 corresponding 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 statistical method first proposed by Lord Rayleigh.

We are therefore compelled to assume, that the classical electrodynamics does not agree with reality, or expressed more carefully, that it cannot 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 radiation which was in good agreement with the results of experiment. Planck did not limit himself exclusively to the classical electrodynamics, 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 discontinuously. 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

, where

is Planck's constant and

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 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 transformation of energy, for with the aid of Planck's constant

it seems to be possible, at least approximately, to account for a great number of phenomena about which nothing could be said previously. It is 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

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 characteristic feature of Rutherford's theory is the assumption of the existence of a positively charged nucleus inside the atom. A number 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 atom is exactly equal to this number. This hypothesis, which was first stated by van den Broek (1912), opens the possibility of obtaining a simple explanation of the periodic system. This assumption is strongly confirmed by experiments on the elements of small atomic weight. In the first place, it is evident that according to Rutherford's theory the

particle is the same as the nucleus of a helium atom. Since the

particle has a double positive charge it follows immediately that a neutral helium atom contains two electrons. Further the concordant results obtained from calculations based on experiments as different as the diffuse scattering of X-rays and the decrease in velocity of

rays in passing through matter render the conclusion extremely likely that a hydrogen atom contains only a single electron. This agrees most beautifully with the fact that J. J. Thomson in his well-known experiments on rays of positive electricity has never observed a 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, still less its line spectrum, on the basis of considerations relating 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 accelerated 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 by

, and the major axis of the ellipse by

we find that

where

is the charge of the electron and

its mass, while

is 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

, and are independent of the eccentricity of the orbit. By varying

we may obtain all possible values for

and

. 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 cannot 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

and

alone it is impossible to obtain a quantity which can be 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

would continually increase, and the above expressions (4) show that at the same time the frequency of revolution of the system would increase, and the dimensions of the orbit decrease. This process would not stop until the particles had approached 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

), and of the nucleus as calculated by Rutherford (about

), this energy would be many times greater than the energy changes with which we are familiar in 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 explanation of the experiments on temperature radiation with the aid of electrodynamics, no matter what atomic model be employed. The fact that the deficiencies of the atomic model we are considering stand out so plainly is therefore perhaps no serious drawback; even though the defects of other atomic models are 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 application of Planck's theory. This theory is concerned with the emission and absorption of energy in a system of electrical particles, which oscillate with a given frequency per second, dependent only on the nature of the system and independent of the amount of energy contained in the system. In a system consisting of an electron and a nucleus the period of oscillation corresponds to the period of revolution of the electron. But the formula (4) for

shows that the frequency of revolution depends upon

, i.e. on the energy of the system. Still the fact that we cannot 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 cannot 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 energy over oscillations of the various wave lengths. Even though we may assume that this energy comes from systems of oscillating particles, we know little or nothing about 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

, where

is Planck's constant and

is the frequency of the radiation. Indeed, it is possible to derive Planck's law of radiation 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 let us 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 corresponding to the frequency

it will be assumed that one of the atoms of the element (or some other elementary system) can emit an amount of energy

. Denoting the energy of the atom before and after the emission of the radiation by

we have

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 shall call them "stationary" states, simply indicating thereby that they form some kind of waiting places between which occurs the emission of the energy corresponding to the various spectral 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

, where

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

respectively. Using this interpretation the combination principle asserts that a series of stationary states exists for the given system, and that it can 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

According to our assumption this spectrum is produced by transitions 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

th state, apart from an additive constant, is given by

. Let us now try 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 at least, no other means available besides the ordinary mechanics.

Corresponding to the

th stationary state in formula (4) for

, let us by way of experiment put

. 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 relation 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 how or why the radiation is emitted. On one point, however, we may expect a connection with the ordinary conceptions; namely, that it will be possible to calculate the emission of slow electromagnetic 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

it is seen that the frequency of revolution decreases as

increases, and that the expression

approaches the value

.

According to what has been said above, the frequency of the radiation corresponding to the transition between the

th and the

th stationary state is given by

If

is very large this expression is approximately equal to

In order to obtain a connection with the ordinary electrodynamics let us now place this frequency equal to the frequency of revolution, that is

Introducing this value of

in (6) we see that

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

The constant

is very accurately known, and is, as I have said before, equal to

. By introducing the most recent values for

,

and

the expression on the right-hand side of the equation becomes equal to

. The agreement is as good as could be expected, considering the uncertainty in the experimental determination of the constants

,

and

. The agreement between our calculations and the classical electrodynamics is, therefore, fully as good as we are justified in expecting.

We cannot 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 states. By introducing the expression, which has been found for

, we get for the

th state

. This equation is entirely analogous to Planck's assumption concerning the energy of a resonator.

in our system is readily shown to be equal to the average value of the kinetic energy of the electron during a single revolution. The energy of a resonator was shown by Planck you may remember to be always equal to

. Further the average value of the kinetic energy of Planck's resonator is equal to its potential energy, so that the average value of the kinetic energy of the resonator, according to Planck, is equal to

. This analogy suggests another manner of presenting the theory, and it was just in this way that I was originally led into these considerations. 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 given I have tried to free myself as much as possible from it.

Let us continue with the elucidation of the calculations, and in the expression for

introduce the value of

which corresponds to the

th stationary state. This gives us

It is seen that for small values of

, 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

,

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

. For this state

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 cannot be transferred except by adding energy to it from without. The large values for

corresponding to large

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

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 forces from the neighbouring atoms the pressure will have to be very low, so low, indeed, that it is impossible to obtain sufficient light from a Geissler tube of ordinary dimensions. In the stars, however, we may assume that we have to do with hydrogen which is exceedingly attenuated and distributed throughout an enormously large region of space.

The Pickering lines. You have probably noticed that we have not mentioned at all the spectrum found in certain stars which according to the opinion then current was assigned to hydrogen, and together with the ordinary hydrogen spectrum was considered by Rydberg to form a connected system of lines completely analogous to the spectra of other elements. You have probably also perceived that difficulties would arise in interpreting this spectrum by means of the assumptions which have been employed. If such an attempt were to be made it would be necessary to give up the simple considerations which lead to the expression (7) for the constant

. We shall see, however, that it appears possible to explain the occurrence of this spectrum in another way. Let us suppose that it is not due to hydrogen, but to some other simple system consisting of a single electron revolving about a nucleus with an electrical charge

. The expression for

becomes then

Repeating the same calculations as before only in the inverse order we find, that this system will emit a line spectrum given by the expression

By comparing this formula with the formula for Pickering's and Rydberg's series, we see that the observed lines can be explained on the basis of the theory, if it be assumed that the spectrum is due to an electron revolving about a nucleus with a charge

, or according to Rutherford's theory around the nucleus of a helium atom. The fact that the spectrum in question is not observed in an ordinary helium tube, but only in stars, may be accounted for by the high degree of ionization which is required for the production of this spectrum; a neutral helium atom contains of course two electrons while the system under consideration contains only one.

These conclusions appear to be supported by experiment. Fowler, as I have mentioned, has recently succeeded in observing Pickering's and Rydberg's lines in a laboratory experiment. By passing a very heavy current through a mixture of hydrogen and helium Fowler observed not only these lines but also a new series of lines. This new series was of the same general type, the wave length being given approximately by

Fowler interpreted all the observed lines as the hydrogen spectrum sought for. With the observation of the latter series of lines, however, the basis of the analogy between the hypothetical hydrogen spectrum and the other spectra disappeared, and thereby also the foundation upon which Rydberg had founded his conclusions; on the contrary it is seen, that the occurrence of the lines was exactly what was to be expected on our view.

In the following table the first column contains the wave lengths measured by Fowler, while the second contains the limiting values of the experimental errors given by him; in the third column we find the products of the wave lengths by the quantity

; the values employed for

and

are enclosed in parentheses in the last column.

4685.98 0.01 22779.1 (3 : 4)
3203.30 0.05 22779.0 (3 : 5)
2733.34 0.05 22777.8 (3 : 6)
2511.31 0.05 22778.3 (3 : 7)
2385.47 0.05 22777.9 (3 : 8)
2306.20 0.10 22777.3 (3 : 9)
2252.88 0.10 22779.1 (3 : 10)
5410.5 1.0 22774 (4 : 7)
4541.3 0.25 22777 (4 : 9)
4200.3 0.5 22781 (4 : 11)

The values of the products are seen to be very nearly equal, while the deviations are of the same order of magnitude as the limits of experimental error. The value of the product

should for this spectrum, according to the formula (9), be exactly

of the corresponding product for the hydrogen spectrum. From the tables on pages [1] and [16] we find for these products

and

, and dividing the former by the latter we get

. This value is very nearly equal to

; the deviation is, however, much greater than can be accounted for in any way by the errors of the experiments. It has been easy, however, to find a theoretical explanation of this point. In all the foregoing calculations we have assumed that the mass of the nucleus is infinitely great compared to that of the electron. This is of course not the case, even though it holds to a very close approximation; for a hydrogen atom the ratio of the mass of the nucleus to that of the electron will be about

and for a helium atom four times as great.

If we consider a system consisting of an electron revolving about a nucleus with a charge

and a mass

, we find the following expression for the frequency of revolution of the system:

From this formula we find in a manner quite similar to that previously employed that the system will emit a line spectrum, the wave lengths of which are given by the formula

If with the aid of this formula we try to find the ratio of the product for the hydrogen spectrum, to that of the hypothetical helium spectrum we get the value

which is in complete agreement with the preceding value calculated from the experimental observations.

I must further mention that Evans has made some experiments to determine whether the spectrum in question is due to hydrogen or helium. He succeeded in observing one of the lines in very pure helium; there was, at any rate, not enough hydrogen present to enable the hydrogen lines to be observed. Since in any event Fowler does not seem to consider such evidence as conclusive it is to be hoped that these experiments will be continued. There is, however, also another possibility of deciding this question. As is evident from the formula (10), the helium spectrum under consideration should contain, besides the lines observed by Fowler, a series of lines lying close to the ordinary hydrogen lines. These lines may be obtained by putting

, etc. Even if these lines were present, it would be extremely difficult to observe them on account of their position with regard to the hydrogen lines, but should they be observed this would probably also settle the question of the origin of the spectrum, since no reason would seem to be left to assume the spectrum to be due to hydrogen.

Other spectra. For the spectra of other elements the problem becomes more complicated, since the atoms contain a larger number of electrons. It has not yet been possible on the basis of this theory to explain any other spectra besides those which I have already mentioned. On the other hand it ought to be mentioned that the general laws applying to the spectra are very simply interpreted on the basis of our assumptions. So far as the combination principle is concerned its explanation is obvious. In the method we have employed our point of departure was largely determined by this particular principle. But a simple explanation can be also given of the other general law, namely, the occurrence of Rydberg's constant in all spectral formulae. Let us assume that the spectra under consideration, like the spectrum of hydrogen, are emitted by a neutral system, and that they are produced by the binding of an electron previously removed from the system. If such an electron revolves about the nucleus in an orbit which is large in proportion to that of the other electrons it will be subjected to forces much the same as the electron in a hydrogen atom, since the inner electrons individually will approximately neutralize the effect of a part of the positive charge of the nucleus. We may therefore assume that for this system there will exist a series of stationary states in which the motion of the outermost electron is approximately the same as in the stationary states of a hydrogen atom. I shall not discuss these matters any further, but shall only mention that they lead to the conclusion that Rydberg's constant is not exactly the same for all elements. The expression for this constant will in fact contain the factor

, where

is the mass of the nucleus. The correction is exceedingly small for elements of large atomic weight, but for hydrogen it is, from the point of view of spectrum analysis, very considerable. If the procedure employed leads to correct results, it is not therefore permissible to calculate Rydberg's constant directly from the hydrogen spectrum; the value of the universal constant should according to the theory be

and not

.

I shall not tire you any further with more details; I hope to return to these questions here in the Physical Society, and to show how, on the basis of the underlying ideas, it is possible to develop a theory for the structure of atoms and molecules. Before closing I only wish to say that I hope I have expressed myself sufficiently clearly so that you have appreciated the extent to which these considerations conflict with the admirably coherent group of conceptions which have been rightly termed the classical theory of electrodynamics. On the other hand, by emphasizing this conflict, I have tried to convey to you the impression that it may be also possible in the course of time to discover a certain coherence in the new ideas.

[1] Address delivered before the Physical Society in Copenhagen, Dec. 20, 1913.

ESSAY II[2]
ON THE SERIES SPECTRA OF THE ELEMENTS