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Mathematical Proceedings of the Cambridge Philosophical Society

The Wave Mechanics of an Atom with a Non-Coulomb Central Field. Part IV. Further Results relating to Terms of the Optical Spectrum

Douglas Rayner Hartree

Published Jul 1, 1929• 30 citations
Publisher

Abstract

The purpose of this note is to extend in two respects some previous work of the writer on the wave equation of a particle in a central field of force which is a Coulomb field for sufficiently large r.
DOI
10.1017/s0305004100014031

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Abstract 1. In a recent paper Dirac* has brilliantly removed the defects before existing in the mechanics of the electron, and has shown how the phenomena usually called the “ spinning electron ” fit into place in the complete theory. He applies to he problem the method of q-numbers and, using non-commutative algebra, exhibits the properties of a free electron, and of an electron in a central field of electric force. In a second paper † he also discusses the rules of combination and the Zeeman effect. There are probably readers who will share the present writer’s feeling that the methods of non-commutative algebra are harder to follow, and certainly much more difficult to invent, than are operations of types long familiar to analysis. Wherever it is possible to do so, it is surely better to present the theory in a mathematical form that dates from the time of Laplace and Legendre, if only because the details of the calculus have been so much more thoroughly explored. So the object of the present work is to take Dirac’s system and treat it by the ordinary methods of wave calculus. The chief point of interest is perhaps the solution of the problem of the central field, which can be carried out exactly and leads to Sommerfeld’s original formula for the hydrogen levels. But it is also of some interest to exhibit the relationship of the new theory to the previous equations which were derived empirically by the present writer.* It appears that those equations were an approximation to the new ones, derived by an approximate elimination of two of Dirac’s four wave functions. We shall also review a few other points connected with the free electron, the emission of radiation from an atom and its magnetic moment, and shall outline a discussion of the Zeeman effect.

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In two recent papers the writer has given an account of a practical method of finding the characteristic values and functions of Schrödinger's wave equations for a given non-Coulomb central field. For terms of optical spectra the method is effectively the following. We take the wave equation in the form and require the values of ɛ for the solutions which are zero at the origin and at r = ∞. We consider the result of integrating this equation outwards from P = 0 at r = 0 to a radius r0 at which the deviation from a Coulomb field is negligible, and inwards from P = 0 at r = ∞ to the same radius, with a given value of ɛ; the characteristic values are those values for which these two solutions join smoothly on to one another, i.e. for which they have the same value of η = −P′/P at this radius. For a given ɛ, the solution zero at the origin depends on the particular atom; the solution zero at infinity can be expressed in a form independent of any particular atom.
It is shown that a wave mechanical quantum theory can be derived from relativistic classical electrodynamics, as a feature of the magnetic interaction of Dirac particles modeled as relativistically circulating point charges. The magnetic force between two classical point charges, each undergoing relativistic circulatory motion of small radius compared to the separation between their centers of circulation, and assuming a time-symmetric electromagnetic interaction, is modulated by a factor that behaves similarly to the Schrödinger wavefunction. The magnetic force between relativistically-circulating charges has been shown previously to have a radially-directed inverse-square part of similar strength to the Coulomb force, and sinusoidally modulated by the phase difference of the charges' circulatory motions. The magnetic force modulation in the case of relatively moving centers of charge circulation solves an equation formally identical to the time-dependent free-particle Schrödinger equation, apart from a factor of two on the partial time derivative term. Considering motion in a time-independent potential obtains that the modulation also satisfies an equation formally similar to the time-independent Schrodinger equation. Using a formula for relativistic rest energy advanced by Osiak, the time-independent Schrödinger equation is solved exactly by the resulting modulation function. The significance of the quantum mechanical wavefunction follows straightforwardly from these observations. After considering the modification of Wheeler-Feynman absorber theory required by the adoption of Minkowski-Osiak relativity, the model is extended to obtain the full complex Schrödinger wavefunction.
Abstract 1. In a recent paper Dirac* has brilliantly removed the defects before existing in the mechanics of the electron, and has shown how the phenomena usually called the “ spinning electron ” fit into place in the complete theory. He applies to he problem the method of q-numbers and, using non-commutative algebra, exhibits the properties of a free electron, and of an electron in a central field of electric force. In a second paper † he also discusses the rules of combination and the Zeeman effect. There are probably readers who will share the present writer’s feeling that the methods of non-commutative algebra are harder to follow, and certainly much more difficult to invent, than are operations of types long familiar to analysis. Wherever it is possible to do so, it is surely better to present the theory in a mathematical form that dates from the time of Laplace and Legendre, if only because the details of the calculus have been so much more thoroughly explored. So the object of the present work is to take Dirac’s system and treat it by the ordinary methods of wave calculus. The chief point of interest is perhaps the solution of the problem of the central field, which can be carried out exactly and leads to Sommerfeld’s original formula for the hydrogen levels. But it is also of some interest to exhibit the relationship of the new theory to the previous equations which were derived empirically by the present writer.* It appears that those equations were an approximation to the new ones, derived by an approximate elimination of two of Dirac’s four wave functions. We shall also review a few other points connected with the free electron, the emission of radiation from an atom and its magnetic moment, and shall outline a discussion of the Zeeman effect.