The Dreams That Stuff is Made of
Page 11
“In any 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 every electron round the centre of its orbit will in the permanent state of the system be equal to h/(2π), where h is Planck’s constant”bl.
In analogy with the considerations on p. 23, we shall assume that a configuration satisfying this condition is stable if the total energy of the system is less then in any neighbouring configured satisfying the same condition of the angular momentum of the electrons.
As mentioned in the introduction, the above hypothesis will be used in a following communication as a basis for a theory of the constitution of atoms and molecules. It will be shown that it leads to results which seem to be in conformity with experiments on a number of different phenomena.
The foundation of the hypothesis has been sought entirely in its relation with Planck’s theory of radiation; by help of considerations given later it will be attempted to throw some further light on the foundation of it from another point of view.
April 5, 1913
THE STRUCTURE OF THE ATOM
BY
NIELS BOHR
Nobel Lecture, December 11, 1922
Ladies and Gentlemen. Today, as a consequence of the great honour the Swedish Academy of Sciences has done me in awarding me this year’s Nobel Prize for Physics for my work on the structure of the atom, it is my duty to give an account of the results of this work and I think that I shall be acting in accordance with the traditions of the Nobel Foundation if I give this report in the form of a survey of the development which has taken place in the last few years within the field of physics to which this work belongs.
The general picture of the atom
The present state of atomic theory is characterized by the fact that we not only believe the existence of atoms to be proved beyond a doubt, but also we even believe that we have an intimate knowledge of the constituents of the individual atoms. I cannot on this occasion give a survey of the scientific developments that have led to this result; I will only recall the discovery of the electron towards the close of the last century, which furnished the direct verification and led to a conclusive formulation of the conception of the atomic nature of electricity which had evolved since the discovery by Faraday of the fundamental laws of electrolysis and Berzelius’s electrochemical theory, and had its greatest triumph in the electrolytic dissociation theory of Arrhenius. This discovery of the electron and elucidation of its properties was the result of the work of a large number of investigators, among whom Lenard and J. J. Thomson may be particularly mentioned. The latter especially has made very important contributions to our subject by his ingenious attempts to develop ideas about atomic constitution on the basis of the electron theory. The present state of our knowledge of the elements of atomic structure was reached, however, by the discovery of the atomic nucleus, which we owe to Rutherford, whose work on the radioactive substances discovered towards the close of the last century has much enriched physical and chemical science.
According to our present conceptions, an atom of an element is built up of a nucleus that has a positive electrical charge and is the seat of by far the greatest part of the atomic mass, together with a number of electrons, all having the same negative charge and mass, which move at distances from the nucleus that are very great compared to the dimensions of the nucleus or of the electrons themselves. In this picture we at once see a striking resemblance to a planetary system, such as we have in our own solar system. Just as the simplicity of the laws that govern the motions of the solar system is intimately connected with the circumstance that the dimensions of the moving bodies are small in relation to the orbits, so the corresponding relations in atomic structure provide us with an explanation of an essential feature of natural phenomena in so far as these depend on the properties of the elements. It makes clear at once that these properties can be divided into two sharply distinguished classes.
To the first class belong most of the ordinary physical and chemical properties of substances, such as their state of aggregation, colour, and chemical reactivity. These properties depend on the motion of the electron system and the way in which this motion changes under the influence of different external actions. On account of the large mass of the nucleus relative to that of the electrons and its smallness in comparison to the electron orbits, the electronic motion will depend only to a very small extent on the nuclear mass, and will be determined to a close approximation solely by the total electrical charge of the nucleus. Especially the inner structure of the nucleus and the way in which the charges and masses are distributed among its separate particles will have a vanishingly small influence on the motion of the electron system surrounding the nucleus. On the other hand, the structure of the nucleus will be responsible for the second class of properties that are shown in the radioactivity of substances. In the radioactive processes we meet with an explosion of the nucleus, whereby positive or negative particles, the so-called α- and β-particles, are expelled with very great velocities.
Our conceptions of atomic structure afford us, therefore, an immediate explanation of the complete lack of interdependence between the two classes of properties, which is most strikingly shown in the existence of substances which have to an extraordinarily close approximation the same ordinary physical and chemical properties, even though the atomic weights are not the same, and the radioactive properties are completely different. Such substances, of the existence of which the first evidence was found in the work of Soddy and other investigators on the chemical properties of the radioactive elements, are called isotopes, with reference to the classification of the elements according to ordinary physical and chemical properties. It is not necessary for me to state here how it has been shown in recent years that isotopes are found not only among the radioactive elements, but also among ordinary stable elements; in fact, a large number of the latter that were previously supposed simple have been shown by Aston’s well-known investigations to consist of a mixture of isotopes with different atomic weights.
The question of the inner structure of the nucleus is still but little understood, although a method of attack is afforded by Rutherford’s experiments on the disintegration of atomic nuclei by bombardment with a-particles. Indeed, these experiments may be said to open up a new epoch in natural philosophy in that for the first time the artificial transformation of one element into another has been accomplished. In what follows, however, we shall confine ourselves to a consideration of the ordinary physical and chemical properties of the elements and the attempts which have been made to explain them on the basis of the concepts just outlined.
It is well known that the elements can be arranged as regards their ordinary physical and chemical properties in a natural system which displays most suggestively the peculiar relationships between the different elements. It was recognized for the first time by Mendeleev and Lothar Meyer that when the elements are arranged in an order which is practically that of their atomic weights, their chemical and physical properties show a pronounced periodicity. A diagrammatic representation of this so-called Periodic Table is given in Fig. 1, where, however, the elements are not arranged in the ordinary way but in a somewhat modified form of a table first given by Julius Thomsen, who has also made important contributions to science in this domain. In the figure the elements are denoted by their usual chemical symbols, and the different vertical columns indicate the so-called periods. The elements in successive columns which possess homologous chemical and physical properties are connected with lines. The meaning of the square brackets around certain series of elements in the later periods, the properties of which exhibit typical deviations from the simple periodicity in the first periods, will be discussed later.
FIG. 1
In the development of the theory of atomic structure the characteristic features of the natural system have found a surprisingly simple interpretation. Thus we a
re led to assume that the ordinal number of an element in the Periodic Table, the so-called atomic number, is just equal to the number of electrons which move about the nucleus in the neutral atom. In an imperfect form, this law was first stated by Van den Broek; it was, however, foreshadowed by J. J. Thomson’s investigations of the number of electrons in the atom, as well as by Rutherford’s measurements of the charge on the atomic nucleus. As we shall see, convincing support for this law has since been obtained in various ways, especially by Moseley’s famous investigations of the X-ray spectra of the elements. We may perhaps also point out, how the simple connexion between atomic number and nuclear charge offers an explanation of the laws governing the changes in chemical properties of the elements after expulsion of α- or β-particles, which found a simple formulation in the so-called radioactive displacement law.
Atomic stability and electrodynamic theory
As soon as we try to trace a more intimate connexion between the properties of the elements and atomic structure, we encounter profound difficulties, in that essential differences between an atom and a planetary system show themselves here in spite of the analogy we have mentioned.
The motions of the bodies in a planetary system, even though they obey the general law of gravitation, will not be completely determined by this law alone, but will depend largely on the previous history of the system. Thus the length of the year is not determined by the masses of the sun and the earth alone, but depends also on the conditions that existed during the formation of the solar system, of which we have very little knowledge. Should a sufficiently large foreign body some day traverse our solar system, we might among other effects expect that from that day the length of the year would be different from its present value.
It is quite otherwise in the case of atoms. The definite and unchangeable properties of the elements demand that the state of an atom cannot undergo permanent changes due to external actions. As soon as the atom is left to itself again, its constituent particles must arrange their motions in a manner which is completely determined by the electric charges and masses of the particles. We have the most convincing evidence of this in spectra, that is, in the properties of the radiation emitted from substances in certain circumstances, which can be studied with such great precision. It is well known that the wavelengths of the spectral lines of a substance, which can in many cases be measured with an accuracy of more than one part in a million, are, in the same external circumstances, always exactly the same within the limit of error of the measurements, and quite independent of the previous treatment of this substance. It is just to this circumstance that we owe the great importance of spectral analysis, which has been such an invaluable aid to the chemist in the search for new elements, and has also shown us that even on the most distant bodies of the universe there occur elements with exactly the same properties as on the earth.
On the basis of our picture of the constitution of the atom it is thus impossible, so long as we restrict ourselves to the ordinary mechanical laws, to account for the characteristic atomic stability which is required for an explanation of the properties of the elements.
The situation is by no means improved if we also rake into consideration the well-known electrodynamic laws which Maxwell succeeded in formulating on the basis of the great discoveries of Oersted and Faraday in the first half of the last century. Maxwell’s theory has not only shown itself able to account for the already known electric and magnetic phenomena in all their details, but has also celebrated its greatest triumph in the prediction of the electromagnetic waves which were discovered by Hertz, and are now so extensively used in wireless telegraphy.
For a time it seemed as though this theory would also be able to furnish a basis for an explanation of the details of the properties of the elements, after it had been developed, chiefly by Lorentz and Larmor, into a form consistent with the atomistic conception of electricity. I need only remind you of the great interest that was aroused when Lorentz, shortly after the discovery by Zeeman of the characteristic changes that spectral lines undergo when the emitting substance is brought into a magnetic field, could give a natural and simple explanation of the main features of the phenomenon. Lorentz assumed that the radiation which we observe in a spectral line is sent out from an electron executing simple harmonic vibrations about a position of equilibrium, in precisely the same manner as the electromagnetic waves in radiotelegraphy are sent out by the electric oscillations in the antenna. He also pointed out how the alteration observed by Zeeman in the spectral lines corresponded exactly to the alteration in the motion of the vibrating electron which one would expect to be produced by the magnetic field.
It was, however, impossible on this basis to give a closer explanation of the spectra of the elements, or even of the general type of the laws holding with great exactness for the wavelengths of lines in these spectra, which had been established by Balmer, Rydberg, and Ritz. After we obtained details as to the constitution of the atom, this difficulty became still more manifest; in fact, so long as we confine ourselves to the classical electrodynamic theory we cannot even understand why we obtain spectra consisting of sharp lines at all. This theory can even be said to be incompatible with the assumption of the existence of atoms possessing the structure we have described, in that the motions of the electrons would claim a continuous radiation of energy from the atom, which would cease only when the electrons had fallen into the nucleus.
The origin of the quantum theory
It has, however, been possible to avoid the various difficulties of the electrodynamic theory by introducing concepts borrowed from the so-called quantum theory, which marks a complete departure from the ideas that have hitherto been used for the explanation of natural phenomena. This theory was originated by Planck, in the year 1900, in his investigations on the law of heat radiation, which, because of its independence of the individual prop erties of substances, lent itself peculiarly well to a test of the applicability of the laws of classical physics to atomic processes.
Planck considered the equilibrium of radiation between a number of systems with the same properties as those on which Lorentz had based his theory of the Zeeman effect, but he could now show not only that classical physics could not account for the phenomena of heat radiation, but also that a complete agreement with the experimental law could be obtained if—in pronounced contradiction to classical theory—it were assumed that the energy of the vibrating electrons could not change continuously, but only in such a way that the energy of the system always remained equal to a whole number of so-called energy-quanta. The magnitude of this quantum was found to be proportional to the frequency of oscillation of the particle, which, in accordance with classical concepts, was supposed to be also the frequency of the emitted radiation. The proportionality factor had to be regarded as a new universal constant, since termed Planck’s constant, similar to the velocity of light, and the charge and mass of the electron.
Planck’s surprising result stood at first completely isolated in natural science, but with Einstein’s significant contributions to this subject a few years after, a great variety of applications was found. In the first place, Einstein pointed out that the condition limiting the amount of vibrational energy of the particles could be tested by investigation of the specific heat of crystalline bodies, since in the case of these we have to do with similar vibrations, not of a single electron, but of whole atoms about positions of equilibrium in the crystal lattice. Einstein was able to show that the experiment confirmed Planck’s theory, and through the work of later investigators this agreement has proved quite complete. Furthermore, Einstein emphasized another consequence of Planck’s results, namely, that radiant energy could only be emitted or absorbed by the oscillating particle in so-called “quanta of radiation”, the magnitude of each of which was equal to Planck’s constant multiplied by the frequency.
In his attempts to give an interpretation of this result, Einstein was led to the formulation of the so-called “hypothesis
of light-quanta”, according to which the radiant energy, in contradiction to Maxwell’s electromagnetic theory of light, would not be propagated as electromagnetic waves, but rather as concrete light atoms, each with an energy equal to that of a quantum of radiation. This concept led Einstein to his well-known theory of the photoelectric effect. This phenomenon, which had been entirely unexplainable on the classical theory, was thereby placed in a quite different light, and the predictions of Einstein’s theory have received such exact experimental confirmation in recent years, that perhaps the most exact determination of Planck’s constant is afforded by measurements on the photoelectric effect. In spite of its heuristic value, however, the hypothesis of light-quanta, which is quite irreconcilable with so-called interference phenomena, is not able to throw light on the nature of radiation. I need only recall that these interference phenomena constitute our only means of investigating the properties of radiation and therefore of assigning any closer meaning to the frequency which in Einstein’s theory fixes the magnitude of the light-quantum.
In the following years many efforts were made to apply the concepts of the quantum theory to the question of atomic structure, and the principal emphasis was sometimes placed on one and sometimes on the other of the consequences deduced by Einstein from Planck’s result. As the best known of the attempts in this direction, from which, however, no definite results were obtained, I may mention the work of Stark, Sommerfeld, Hasenöhrl, Haas, and Nicholson.