The Bohr formulation—the original one—is now largely a matter of history. The usual career of a theory was its fate. It explained much, but it failed at the first signs of complication, even for the simplest molecules as hydrogen and helium. Some results were either only approximate in a loose or incomplete fashion, e.g. in the application of the correspondence principle to intensities, the only reliable predictions being only for an absence of certain lines, or they quite disagreed with experiment, e.g. in the case of the hydrogen molecule and the hydrogen molecule ion, the normal and excited states of helium, the anomalous Zeeman effect, the Ramsauer effect (the phenomenon of the deflection of electrons at low speeds being less than at higher speeds in atomic collisions), and in the treatment of problems where more than one electron was involved. In the last mentioned cases the perturbation method, so successful in solving “many-body” problems in celestial mechanics, failed completely because systems of several electrons, possessing frequencies of the order of light waves, cannot interact classically. A bit of much forced pragmatism was practiced in treating the many electron atom as a variation of the hydrogen atom. Besides, there were technical oddities, like ½ quantum numbers, and impenetrated anologies between visible and X-ray spectra.
The Bohr formulation—the original one—is now largely a matter of history. The usual career of a theory was its fate. It explained much, but it failed at the first signs of complication, even for the simplest molecules as hydrogen and helium. Some results were either only approximate in a loose or incomplete fashion, e.g. in the application of the correspondence principle to intensities, the only reliable predictions being only for an absence of certain lines, or they quite disagreed with experiment, e.g. in the case of the hydrogen molecule and the hydrogen molecule ion, the normal and excited states of helium, the anomalous Zeeman effect, the Ramsauer effect (the phenomenon of the deflection of electrons at low speeds being less than at higher speeds in atomic collisions), and in the treatment of problems where more than one electron was involved. In the last mentioned cases the perturbation method, so successful in solving “many-body” problems in celestial mechanics, failed completely because systems of several electrons, possessing frequencies of the order of light waves, cannot interact classically. A bit of much forced pragmatism was practiced in treating the many electron atom as a variation of the hydrogen atom. Besides, there were technical oddities, like ½ quantum numbers, and impenetrated anologies between visible and X-ray spectra.
Abstract Bohr’s theory of the atom did a fine job of explaining the absorption and em1ss10n spectra of one-electron atoms in terms of the quantum rules. Schrodinger’s wave mechanics did better in the sense that the rules of quantization were given a firm mathematical basis. However, problems still abounded. Experimental spectra revealed quite a number of problems for which wave mechanics (and matrix mechanics) appeared to have no solutions. In particular, some atomic emission lines predicted by the theory were seen to be split in the presence of a magnetic field into several quite distinct lines (a phenomenon known as the Zeeman effect). Neither wave mechanics nor matrix mechanics could explain this phenomenon without some further, largely ad hoc, assumptions. Worse still, when the spectra of atoms with two or more electrons were studied, certain predicted lines were found to be missing.
The new physics just described was still based largely on Newtonian ideas. Indeed, in its theoretical aspects, it might not unfairly be described as a final attempt to explain the world in materialistic terms—as particles being pushed and pulled about in space and time. Nevertheless, the new physics had found it necessary to abolish most of the forces of pushing and pulling, replacing the gradual changes of motion of the particles under these forces by sudden and unpredictable jumps. These appeared to involve violations of the law of causality, both in the disintegration of radioactive atoms and also in the internal changes of ordinary atoms. We seemed to see Fate defying this law as she picked out certain atoms for disintegration or collapse and, by her apparently capricious acts, sent the universe along one path or another according to her whim. On such lines the new physics had explained many phenomena which had hitherto seemed inexplicable, but it had by no means met with complete success. For instance, while it gave a perfect interpretation of the simplest spectrum of all, namely that of the hydrogen atom, it failed with more complex spectra. This was not necessarily a fatal objection; a few emendations and possibly a few new ad hoc assumptions might have effected a complete reconciliation, although this seems improbable.
Abstract In a previous paper the theory of perturbations was discussed for system which possess only discrete spectra. The theory is now extended to systems with both discrete and continuous spectra, and in addition a slightly more general method of perturbation is considered. The Hamiltonian H of the perturbed systems is split up into three parts H0, H1, H2 (t), two of which can be chosen arbitrarily. The solutions of the perturbed problem can then be worked out in terms of the characteristic functions corresponding to the Hamiltonian H0 + H2 (T), where T is any arbitrary fixed time. In general, however, the series of perturbations does not converge, and different modes of splitting up the Hamiltonian will lead to different formal results. The perturbation theory does usually give the correct physical results, and it is therefore necessary to give some explanation of how this happens. In (I) the asymptotic nature of certain solutions was emphasised, but this does not extend to the more general systems treated here. It is suggested that the usual boundary conditions do not give an adequate description of any but the simplest atomic problems, and that more detailed restrictions, determined by the experimental conditions, ought to be substituted. As this is impossible in practice, an alternative method is to regard the motion as a perturbation on that Hamiltonian H0 + H2 (T) which most nearly corresponds to the experimental conditions. (For example, we may regard an electron as free or bound according as the experiment determines the number of free or bound electrons respectively, whereas in the usual theory the initial Hamiltonian is taken as fundamental.) This criterion, together with the initial conditions, suffices to fix the division of H into the three parts H0, H1, H2 (t) which at first were chosen arbitrarily. The formal solution can be worked out on this basis, and it is then assumed that this solution is asymptotic to the one which would be obtained if the full boundary conditions were used. This suggestion is in accordance with the fact that a hydrogen atom in an electric field gives rise not only to the usual Stark effect, but also to an ionisation effect. In § 2 the perturbation equation are derived in a slightly more general form than has previously been given. The theories of Born,* Dirac and Oppenheimer are particular cases of that given here, and are obtained by particular choices of H0, H1, H2 (t). To obtain Born’s theory we take H1 = 0, and for Oppenheimer’s we take H2 (t) = H2 (T) and T = 0. In Dirac’s theory we have H1 = 0, H2 (0) = 0 and T = 0. Each of these theories is appropriate for the solution of special problems, but the more general method of this paper is required for the full discussion of the perturbation theory.
The founding fathers of quantum mechanics had already perceived the essence of the difficulties of quantum mechanics; today, after almost a century, the discussions are still lively and, if some very interesting new aspects have emerged, at a deeper level the questions have not changed so much. What is more recent, nevertheless, is a general change of attitude among physicists: until about 1970 or 1980, most physicists thought that the essential questions had been settled, and that “Bohr was right and proved his opponents to be wrong”. This was probably a consequence of the famous discussions between Bohr, Einstein, Schrödinger, Heisenberg, Pauli, de Broglie, and others (in particular at the Solvay meetings [1–3], where Bohr's point of view had successfully resisted Einstein's extremely clever attacks). The majority of physicists did not know the details of the arguments. They nevertheless thought that the standard “Copenhagen interpretation” had clearly emerged from the infancy of quantum mechanics as the only sensible attitude for good scientists. This interpretation includes the idea that modern physics must contain indeterminacy as an essential ingredient: it is fundamentally impossible to predict the outcome of single microscopical events; it is impossible to go beyond the formalism of the wave function (or its generalization, the state vector ∣ψ) and complete it.
Abstract An outstanding defect of the old quantum theory was its inability to treat the phenomena occurring in the collision of electrons with atoms, and Born’s theory showed how the new quantum mechanics was capable of removing this defect. The original theory of Born was a method of successive approximations to the solution of the wave equation representing the colliding systems, and could be applied to both elastic and inelastic collisions. In its actual applications, which could be worked out to the first approximation, the theory fell far short of expectations. The Ramsauer effect, the most interesting phenomenon exhibited in the elastic scattering of electrons, could not be explained, and in the field of inelastic collisions, it failed to provide a means of explaining the excitation of levels of a term system which does not combine with the ground state system, e. g., the excitation of the triplet lines of helium. These failures are, of course, failures of the theory in its first approximation. The first approximation in Born’s method of successive approximations neglected the disturbance of the electron waves by the field of the scatterer, and also the possibility of exchange of electrons between the atoms and the colliding beam. The neglect of both these effects becomes important for low velocity impacts, and it was clear that the Ramsauer effect, which is only observed for low velocity electrons, could only be explained by more accurate theory. The question was whether both effects, the distortion of the electron waves by the atomic field, and the exchange of electrons was important, or only one of them.
Bohr theory was not satisfactory as it failed to provide an interpretation of relative line intensities and splitting of spectral lines in the presence of electric field and magnetic field in the hydrogen spectrum. This theory also failed completely when it was applied to explain the energies and spectra of more complex atoms. In this chapter, we consider the application of Schrödinger wave theory to one-electron atom. The simplest one-electron system is the Hydrogen atom, whose Schrödinger equation can be exactly solved. Other one-electron system like He + , Li 2+ etc. can also be solved exactly. The chemical system with more than one-electron cannot be solved exactly due to electron-electron repulsion, which is the most problematic term.