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Physical Review

The Stark Effect from the Point of View of Schroedinger's Quantum Theory

Paul Sophus Epstein

Published Oct 1, 1926• 534 citations
Publisher

Abstract

A theory of the Stark effect based on Schroedinger's ideas is presented. (1) Positions of lines practically coincide with those obtained in the writer's old theory which gave an excellent agreement with experiment. (2) Intensity expressions are obtained in a simple closed form: (a) Components which, in the old theory, had to be ruled out by a special postulate now drop out automatically. (b) The computed intensities of the remaining components check the observed within the limits of experimental error.

DOI
10.1103/physrev.28.695

Related papers

The Stark effect in the Bohr-Sommerfeld theory and in Schrödinger's wave mechanics

Anthony Duncan A, Michel Janssen B

The explanation of the first-order Stark effect in hydrogen by Epstein and Schwarzschild in 1916 was seen as a great success for the old quantum theory. Yet, it also revealed some serious limitations of the theory. To recover the experimentally found line splittings, one had to make some arbitrary assumptions in addition to the basic quantum conditions to rule out certain orbits. The calculation of intensities of lines on the basis of Bohr's correspondence principle likewise required arbitrary additional assumptions. Finally, the actual orbits predicted by the old quantum theory depend on the coordinates chosen to impose the quantum conditions. Both Sommerfeld and Epstein recognized this problem but offered no solution for it. All these problems were solved in 1926 when Schrödinger and Epstein explained the Stark effect on the basis of the new wave mechanics. The calculations in the two theories are similar. In particular, both the Schrödinger equation in the new theory and the Hamilton-Jacobi equation in the old theory are separated in parabolic coordinates. The new quantum mechanics determines all allowed states and transitions without any additional assumptions. It also replaced the ambiguous guidelines based on the correspondence principle for calculating intensities by the straightforward prescription that intensities are given by the squares of the matrix elements of position, leading to results that agreed much better with the experimental data. Finally, the embarrassing non-uniqueness of orbits in the old quantum theory turned into the innocuous non-uniqueness of bases of eigenfunctions in wave mechanics. To this day, the Stark effect is remembered as one of the few qualified successes of the old quantum theory. We suspect that this is largely because after 1926 it became just one of the many unqualified successes of the new quantum theory.

arXiv:1404.5341•Apr 21, 2014•21 citations

On the Theory of the Stark Effect in Hydrogenic Atoms

Vladimir Rojansky

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 $\mathrm{ns}$ and $n{p}_{1}$ 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 $2s$ level in $H$ 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.

Physical Review•Jan 1, 1929•43 citations

The Zeeman effect and spherical harmonics

C. G. DARWIN

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.

Proceedings of the Royal Society of London Series A Containing Papers of a Mathematical and Physical Character•Jun 1, 1927•45 citations

Half-integral quantum numbers in the theory of the stark effect and a general hypothesis of fractional quantum numbers

A. M. Mosharrafa

Abstract 1. Indications of the occurrence of fractional quantum numbers have already been found by Kratzer from a study of certain band spectra, and by Curtis in his experimental investigation of helium bands. Heisenberg has also employed half-integral numbers in a quantum theory of the anomalous Zeeman effect with considerable success. The fourth of the slightly extended quantum conditions recently suggested by W. Wilson and applied by the present writer to the Zeeman effect involves a fractional quantum number, as O. W. Richardson has pointed out. K. F. Niessen, in his work on the positively ionised hydrogen molecule, observes certain discontinuities in the energy graphs between symmetrical and asymmetrical models which strongly the occurrence of half-integral quantum orbits for the latter. He refrains, however, from making this assumption, on the ground that it would necessitate the adoption of half numbers in the somewhat allied case of the Stark effect.

Proceedings of the Royal Society of London Series A Containing Papers of a Mathematical and Physical Character•Jun 2, 1924•2 citations

A collision problem in the wave mechanics

C. G. DARWIN

Abstract In the present work the wave mechanics are applied to the discussion of a collision problem of a more complicated type than has, I think, hitherto been done. Though there is nothing very new in the process it is rather interesting to see how a wave function behaves which involves two bodies, and is therefore outside our ordinary space intuitions. But the work had a much more general aim, as an attempt to see whether a sharper line of demarcation could be drawn between the particle-like and the wave-like properties of matter. Put briefly, I take a problem which would be regarded at first sight as irreconcilable with a pure wave theory, but thoroughly typical of the behaviour of particles, and show how in fact the correct result arises naturally from the consideration of wave alone. I have been led in this way to certain not very original speculation on the basis of the quantum theory and these are given at the end of the paper. These are not in the least intended to be a general formulation of the theory, but rather as an examination of a particular type of attempted formulation. I fear that the views expressed will be found partly obvious and perhaps partly inconsistent or even erroneous. My excuse for giving them is that the quantum theory seem already sufficiently developed for us to attempt something more than a mathematical formulation of it, and that a generally accepted physical understanding will be more quickly reached by agreement or disagreement with expressed opinions, than by waiting for the arrival of a full-grown theory. It has been an extraordinarily difficult task to express the ideas I intended, and I wish to thank Prof. D. R. Hartree for many valuable criticisms of my first attempts to do so, though he must be exonerated from all blame if the final result is unintelligible or erroneous. 1. The quantum mechanics have been expressed in a variety of ways, which place the emphasis differently, but it has been shown that they are all exactly equivalent, so what may choose which we will. I shall use the following description, limiting myself to the simpler cases which do not involve considerations of relativity. We take a partial differential equation of the wave type, set down according to certain rules depending on the particular system considered. We solve this subject to certain boundary conditions, expressive of all the limitations imposed by silts, mirrors, diffraction, gratings, moving shutters, etc., that may occur in the proposed system, and obtain as result the wave function Ψ, a function of all the co-ordinates of the system and of the time. From this we from a set of functions, of which the simplest is |Ψ|2; this process may be called taking the intensities. We next have to prepare for the particle aspect, by applying certain rules so as to normalise the intensities, a process entirely foreign to the idea of waves. Finally, we make the interpretation, in which we say that the normalised intensities measure the probability of the particles having such and such positions, momenta, energies, etc., and these are the results verified by observation.

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A simple quantum theory of Stark broadening of hydrogen lines including short-range interactions. Application to Ly-α

N. Feautrier, N. Tran Minh

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Journal of Physics B Atomic and Molecular Physics•Dec 1, 1977•10 citations
A theory of the Stark effect based on Schroedinger's ideas is presented. (1) Positions of lines practically coincide with those obtained in the writer's old theory which gave an excellent agreement with experiment. (2) Intensity expressions are obtained in a simple closed form: (a) Components which, in the old theory, had to be ruled out by a special postulate now drop out automatically. (b) The computed intensities of the remaining components check the observed within the limits of experimental error.
The explanation of the first-order Stark effect in hydrogen by Epstein and Schwarzschild in 1916 was seen as a great success for the old quantum theory. Yet, it also revealed some serious limitations of the theory. To recover the experimentally found line splittings, one had to make some arbitrary assumptions in addition to the basic quantum conditions to rule out certain orbits. The calculation of intensities of lines on the basis of Bohr's correspondence principle likewise required arbitrary additional assumptions. Finally, the actual orbits predicted by the old quantum theory depend on the coordinates chosen to impose the quantum conditions. Both Sommerfeld and Epstein recognized this problem but offered no solution for it. All these problems were solved in 1926 when Schrödinger and Epstein explained the Stark effect on the basis of the new wave mechanics. The calculations in the two theories are similar. In particular, both the Schrödinger equation in the new theory and the Hamilton-Jacobi equation in the old theory are separated in parabolic coordinates. The new quantum mechanics determines all allowed states and transitions without any additional assumptions. It also replaced the ambiguous guidelines based on the correspondence principle for calculating intensities by the straightforward prescription that intensities are given by the squares of the matrix elements of position, leading to results that agreed much better with the experimental data. Finally, the embarrassing non-uniqueness of orbits in the old quantum theory turned into the innocuous non-uniqueness of bases of eigenfunctions in wave mechanics. To this day, the Stark effect is remembered as one of the few qualified successes of the old quantum theory. We suspect that this is largely because after 1926 it became just one of the many unqualified successes of the new quantum theory.
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.
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.
Abstract 1. Indications of the occurrence of fractional quantum numbers have already been found by Kratzer from a study of certain band spectra, and by Curtis in his experimental investigation of helium bands. Heisenberg has also employed half-integral numbers in a quantum theory of the anomalous Zeeman effect with considerable success. The fourth of the slightly extended quantum conditions recently suggested by W. Wilson and applied by the present writer to the Zeeman effect involves a fractional quantum number, as O. W. Richardson has pointed out. K. F. Niessen, in his work on the positively ionised hydrogen molecule, observes certain discontinuities in the energy graphs between symmetrical and asymmetrical models which strongly the occurrence of half-integral quantum orbits for the latter. He refrains, however, from making this assumption, on the ground that it would necessitate the adoption of half numbers in the somewhat allied case of the Stark effect.
Abstract In the present work the wave mechanics are applied to the discussion of a collision problem of a more complicated type than has, I think, hitherto been done. Though there is nothing very new in the process it is rather interesting to see how a wave function behaves which involves two bodies, and is therefore outside our ordinary space intuitions. But the work had a much more general aim, as an attempt to see whether a sharper line of demarcation could be drawn between the particle-like and the wave-like properties of matter. Put briefly, I take a problem which would be regarded at first sight as irreconcilable with a pure wave theory, but thoroughly typical of the behaviour of particles, and show how in fact the correct result arises naturally from the consideration of wave alone. I have been led in this way to certain not very original speculation on the basis of the quantum theory and these are given at the end of the paper. These are not in the least intended to be a general formulation of the theory, but rather as an examination of a particular type of attempted formulation. I fear that the views expressed will be found partly obvious and perhaps partly inconsistent or even erroneous. My excuse for giving them is that the quantum theory seem already sufficiently developed for us to attempt something more than a mathematical formulation of it, and that a generally accepted physical understanding will be more quickly reached by agreement or disagreement with expressed opinions, than by waiting for the arrival of a full-grown theory. It has been an extraordinarily difficult task to express the ideas I intended, and I wish to thank Prof. D. R. Hartree for many valuable criticisms of my first attempts to do so, though he must be exonerated from all blame if the final result is unintelligible or erroneous. 1. The quantum mechanics have been expressed in a variety of ways, which place the emphasis differently, but it has been shown that they are all exactly equivalent, so what may choose which we will. I shall use the following description, limiting myself to the simpler cases which do not involve considerations of relativity. We take a partial differential equation of the wave type, set down according to certain rules depending on the particular system considered. We solve this subject to certain boundary conditions, expressive of all the limitations imposed by silts, mirrors, diffraction, gratings, moving shutters, etc., that may occur in the proposed system, and obtain as result the wave function Ψ, a function of all the co-ordinates of the system and of the time. From this we from a set of functions, of which the simplest is |Ψ|2; this process may be called taking the intensities. We next have to prepare for the particle aspect, by applying certain rules so as to normalise the intensities, a process entirely foreign to the idea of waves. Finally, we make the interpretation, in which we say that the normalised intensities measure the probability of the particles having such and such positions, momenta, energies, etc., and these are the results verified by observation.