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Physical Review

The Zeeman Effect and Stark Effect of Hydrogen in Wave Mechanics; The Force Equation and the Virial Theorem in Wave Mechanics

Arthur E. Ruark

Published Apr 1, 1928• 10 citations
Publisher

Abstract

The Zeeman levels of hydrogenic atoms are determined by a new and simple method, neglecting terms in ${\mathrm{H}}^{2}$. The frequency of the Larmor precession is $L={L}_{0}(1+\frac{E}{m{c}^{2}})$. ${L}_{0}$ is the frequency of precession obtained by Newtonian mechanics and $E$ the energy of the atom. This agrees with a formula of Pauli obtained by ordinary relativity mechanics. The formulae for the first order Stark effect and for the Paschen-Back effect can be obtained by similar methods.An extension of Ehrenfest's law of motion for a particle is proved. It is applicable to any conservative system. From it, a theorem of wave mechanics analogous to the virial theorem is obtained.

DOI
10.1103/physrev.31.533

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The Zeeman levels of hydrogenic atoms are determined by a new and simple method, neglecting terms in H2{\mathrm{H}}^{2}H2. The frequency of the Larmor precession is L=L0(1+Emc2)L={L}_{0}(1+\frac{E}{m{c}^{2}})L=L0​(1+mc2E​). L0{L}_{0}L0​ is the frequency of precession obtained by Newtonian mechanics and EEE the energy of the atom. This agrees with a formula of Pauli obtained by ordinary relativity mechanics. The formulae for the first order Stark effect and for the Paschen-Back effect can be obtained by similar methods.An extension of Ehrenfest's law of motion for a particle is proved. It is applicable to any conservative system. From it, a theorem of wave mechanics analogous to the virial theorem is obtained.
The Stark effect of the fine structure of hydrogenic atoms is discussed in the light of the quantum mechanics. Explicit formulas are given for the energy levels in either a weak or a strong electric field, including in each case both the relativity corrections and the Stark effect. (The conventional treatment neglects either one or the other.) The results are, except in form, similar to those recently given by Schlapp. In the new mechanics, in contradistinction to the old Bohr theory, there is a linear Stark effect even in weak fields, because of the identity of energy for the ns\mathrm{ns}ns and np1n{p}_{1}np1​ levels in the absence of external fields. This degeneracy is shown to account for the results of the recent experiments of Ornstein, Zernike, and Snoek, who found that the 2s2s2s level in HHH is not metastable.The coefficients are found for the development of the "parabolic" eigenfunctions in terms of the "polar" ones, and a set of numerical values of these coefficients is tabulated.Methods are given for the calculation of the relative intensities in the Stark effect in terms of the already available theoretical fine structure intensities in the absence of fields.
Niels Bohr’s model of the hydrogen and hydrogen-like atoms, in which the electron is allowed to revolve in certain circular orbits around the nucleus, was extended by Arnold Sommerfeld to allow for the possibility of elliptical orbits. Each elliptical orbit was constrained by two quantization conditions specified by a positive integer nφ and a non-negative integer nr. If, in the presence of the attractive Coulomb force between the electron and the nucleus, the dynamics of the atom were taken to be governed by the Newtonian laws of motion, the energy Ɛ of the two-particle system was found to be a function of the positive integer n = nr + nφ. The atomic energy levels thus exhibited an n-fold degeneracy, which would be lifted in the presence of external electric or magnetic fields, thus accounting for the fine-structure of the spectral lines emitted by the atom—phenomena observed, respectively, in the Stark effect and the Zeeman effect. Sommerfeld also examined the behavior of his elliptical orbits by allowing the revolving electron to obey Einstein’s relativistic dynamics. In this case, the energy-level degeneracies were lifted (even in the absence of external perturbations), and the elliptical orbits were found to precess around the nucleus—similarly to the precession of, say, the orbit of the planet Mercury around the Sun. What is astonishing about Sommerfeld’s relativistic expression of the energy Ɛ as a function of nφ and nr is that it is precisely the same expression as obtained for hydrogen and hydrogen-like atoms from Dirac’s equation, which came more than a decade later. Recall that the spin of the electron was not yet discovered when Sommerfeld developed his model, and that in Dirac’s fully-relativistic quantum mechanics, the spectral fine-structure arises from the coupling of the electron’s spin to its orbital motion. The present paper provides a streamlined yet detailed account of Sommerfeld’s elliptical orbits in hopes of bringing about a deeper appreciation for the miraculous coincidence of Sommerfeld’s result with that derived from Dirac’s equation.
Abstract 1. The chief object of the present paper is to present a simple system of equations which are competent to determine the frequencies and intensities of the lines in the standard Zeeman effect. By the standard Zeeman effect is meant the type where the terms are given by Landé’s "g"and “γ” formulæ, and where the multiplicity of the two sets of terms is the same. It will probably be held that the theory of such multiplets has been fairly completely understood for the last two years owing to the works of Sommerfeld, Heisenberg, Landé and Pauli, and the main new contribution of the present work is that, whereas these writers gave formulæ valid only either in weak or strong field (except for doublets, where Heisenberg and Jordan give the value for any strength), here we have complete formulæ from which the intensity of any component in any strength of field can be obtained merely from the solution of rather simple algebraic equations. The proper attack on this problem would undoubtedly be by way of the recent work of Heisenberg on the helium spectrum, and his still more recent work on complex spectra; but this theory is still in the making, so that it has not been practicable to apply it here, and to this extent our results are unverified. Their validity rests firstly on a complete verification of all known facts connected with both weak and strong fields (and intermediate fields for doublets), and also on a conformity with the general features of wave mechanics. The work of Heisenberg and Jordan could readily have been adapted to give all the results of the present paper; but it would have been harder to follow because the matrix methods are not so easy for most readers as are spherical harmonics.
The linear Stark effect is investigated, using the old quantum theory and the equations of motion of the electron in orbital variables. In contrast to the well-known solution in terms of parabolic coordinates, the new form has a simple geometric interpretation, namely, perturbation by the uniform electric field leads in the first approximation to a slow regular precession of the electron orbit around the direction of the field (subject to a single additional condition). This geometric picture outwardly resembles electron orbits precessing around a uniform magnetic field in the normal Zeeman effect.
The problem of the motion of a particle attracted by two fixed centers of force according to the Coulomb force law can be treated by classical mechanics and has been used in quantum theory by Pauli and Messen for a theory of the hydrogen molecule ion.1 In the quantum mechanics, where the energy levels are determined as the “eigenwerte” of Schrodinger’s equation, the variables are separable and the boundary value problem is easily set up. But thus far a satisfactory treatment of the differential equations involved is lacking. Burrau2 has recently carried out a numerical integration of the problem for the lowest energy level of an electron moving under the influence of two fixed centers of Coulomb attraction as a function of the distance apart of these centers. In this paper, Burrau’s data are used to give a semi-quantitative discussion of the neutral hydrogen molecule. His values are: Nuclear separation 1.0 1.3 1.6 1.8 2.0 2.2 2.4 2.95 Electronic energy 2.896 2.648 2.436 2.309 2.204 2.109 2.025 1.836 The unit of separation is the Bohr l1 orbit radius of hydrogen atom, that of energy is the ionization potential of atomic hydrogen.
The paper gives an account of the author's work on a new form of quantum theory. \textsection{}1. The Hamiltonian analogy between mechanics and optics. \textsection{}2. The analogy is to be extended to include real "physical" or "undulatory" mechanics instead of mere geometrical mechanics. \textsection{}3. The significance of wave-length; macro-mechanical and micro-mechanical problems. \textsection{}4. The wave-equation and its application to the hydrogen atom. \textsection{}5. The intrinsic reason for the appearance of discrete characteristic frequencies. \textsection{}6. Other problems; intensity of emitted light. \textsection{}7. The wave-equation derived from a Hamiltonian variation-principle; generalization to an arbitrary conservative system. \textsection{}8. The wave-function physically means and determines a continuous distribution of electricity in space, the fluctuations of which determine the radiation by the laws of ordinary electrodynamics. \textsection{}9. Non-conservative systems. Theory of dispersion and scattering and of the "transitions" between the "stationary states." \textsection{}10. The question of relativity and the action of a magnetic field. Incompleteness of that part of the theory.