Abstract We consider three topics which proved frustratingly resistant to the methods of the old quantum theory up to the point of emergence of the quantum mechanics of Heisenberg and collaborators in late 1925. First, the old theory could not account convincingly for the superfluity of stationary states implied by the existence of the complex multiplets seen in most atomic spectra. Second, the progressively more complicated theories proposed for explaining the splittings of lines in the anomalous Zeeman effect were found to lead inevitably to glaring inconsistencies with the assumed mechanical equations of motion. Finally, there was the problem of the dual spectrum of helium, and even more basically, of the ground state energy of helium, all calculations of which in terms of specified electron orbits gave incorrect results. We relate the tangled history of the efforts to provide a theoretical resolution of these problems within the old quantum theory.
Abstract We consider three topics which proved frustratingly resistant to the methods of the old quantum theory up to the point of emergence of the quantum mechanics of Heisenberg and collaborators in late 1925. First, the old theory could not account convincingly for the superfluity of stationary states implied by the existence of the complex multiplets seen in most atomic spectra. Second, the progressively more complicated theories proposed for explaining the splittings of lines in the anomalous Zeeman effect were found to lead inevitably to glaring inconsistencies with the assumed mechanical equations of motion. Finally, there was the problem of the dual spectrum of helium, and even more basically, of the ground state energy of helium, all calculations of which in terms of specified electron orbits gave incorrect results. We relate the tangled history of the efforts to provide a theoretical resolution of these problems within the old quantum theory.
Abstract This chapter discusses how the new quantum theory took care of some of the failures of the old quantum theory and how it put the old theory’s successes on a firmer basis. Examples in the former category are the new theory’s resolution of the problems the old theory ran into with the anomalous Zeeman effect and helium (giving the wrong value for its ground state energy and being unable to explain the spectroscopic divide between ortho- and parahelium). Examples in the latter category are the fine structure in hydrogen and the Stark effect. The chapter also discusses some examples of Kuhn losses, instances where the new theory (at least initially) could not account for phenomena explained by the old one.
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 largest failure of the old, Bohr-Sommerfeld quantum theory was with the helium atom. It brought about the theory's demise. I show that this failure does not originate, as commonly believed, with the orbit concept per se. Instead, it was caused by the wrong choice of orbits, compounded by ignorance of the exclusion principle. Choosing semiclassical electron oscillations through the He nucleus, I calculate a singlet ground-state energy that rivals in accuracy with quantum-mechanical results. The same method reveals Bohr's historic energy value as the forbidden triplet ground state--a result beyond the reach of quantum mechanics. At the qualitative level, the concept of Coulomb oscillations visually explains the major features in the He double spectrum in terms of crossed or parallel orbit orientation.
The origin of the new quantum mechanics was an epoch-making memoir by Werner Heisenberg which contained the new concept which was to lead to the phenomenal developments of quantum mechanics of the past two years. Up to this time the quantum theory (the ‘older’ quantum theory) postulated the existence of stationary states of the atom calculated by the use of the classical mechanics and selected by the use of quantum conditions satisfied by the action variables of that theory. In the new mechanics the equations have the same form as in the classical theory, but the variables no longer satisfy the commutative law of multiplication, that is, xy is not in general equal to yx ; the quantum conditions of the older theory are replaced by equations which enable the difference xy – yx to be calculated; these equations involve Planck's constant h. For some years before 1925, Sommerfeld, Heisenberg, Landé and Pauli had been grappling with the complex problem of the multiplets and their Zeeman separations. By the use of a system of quantum numbers l, s, j connected with the respective angular momenta of the series electron, the core, and the whole atom, they had given a qualitative account of the multiplets of the alkalis, alkaline earths, etc., the work culminating in a very general empirical formula—the g -formula of Landé—which enabled the Zeeman separations of a multiplet to be worked out quantitatively in terms of the quantum numbers l, s, j.
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.
Abstract A theory of the helium atom was developed by Heisenberg, following his famous principle of “resonance.” His work is based upon Schrodinger’s equation, and in order to allow for the spin of the electrons he introduces extra energy terms, expressing the classical energy of two appropriate magnets. It is the perturbation by this spin energy which produces the triplet separations. Heisenberg’s calculation of these separations is open to three criticisms: (1) He assumes that certain simple forms are correct first approximations to the wave-functions; whereas, owing to degeneracy, it is necessary to take linear combinations of these forms. (2) He estimates the mean values of the spin energy by means of a model built up of precessing vectors. (3) He neglects the radius of the inner orbit in comparison with that of the outer orbit, even when the principal quantum number of the latter is only 2; this is the least satisfactory of several necessary simplifications. Schrödinger’s equation is likely to be supplanted as the foundation of wave-mechanics by the equation recently put forward by Dirae. This fits the spin of the electron neatly into the theory of relativity, and produces the doublets of the hydrogen-like atom in a beautiful manner. Dirac’s q-number theory has been translated into wave-mechanics by Darwin. Apart altogether from the above criticisms of Heisenberg, it seemed expedient to proceed to the theory of an atom with two electrons on the basis of the new equation. Calculations which are independent of the spin, such as the approximate energylevels, and the separation between ortho- and para-terms, are the same on either theory, and are not the concern of this paper. We deal here with spin effects, such as the fine structure of the triplets and intercombinations between ortho- and para-states.