One of the earliest successes of classical quantum dynamics in a field where ordinary methods had proved inadequate was the solution, by Schwarzschild and Epstein, of the problem of the hydrogen atom in an electric field. It was shown by them that under the influence of the electric field each of the energy levels in which the unperturbed atom can exist on Bohr’s original theory breaks up into a number of equidistant levels whose separation is proportional to the strength of the field. Consequently, each of the Balmer lines splits into a number of components with separations which are integral multiples of the smallest separation. The substitution of the dynamics of special relativity for classical dynamics in the problem of the unperturbed hydrogen atom led Sommerfeld to his well-known theory of the fine-structure of the levels; thus, in the absence of external fields, the state
n
= 1 (
n
= 2 in the old notation) is found to consist of two levels very close together, and
n
= 2 of three, so that the line H
α
of the Balmer series, which arises from a transition between these states, has six fine-structure components, of which three, however, are found to have zero intensity. The theory of the Stark effect given by Schwarzschild and Epstein is adequate provided that the electric separation is so much larger than the fine-structure separation of the unperturbed levels that the latter may be regarded as single; but in weak fields, when this is no longer so, a supplementary investigation becomes necessary. This was carried out by Kramers, who showed, on the basis of Sommerfeld’s original fine-structure theory, that the first effect of a weak electric field is to split each fine-structure level into several, the separation being in all cases proportional to the square of the field so long as this is small. When the field is so large that the fine-structure is negligible in comparison with the electric separation, the latter becomes proportional to the first power of the field, in agreement with Schwarzschild and Epstein. The behaviour of a line arising from a transition between two quantum states will be similar; each of the fine-structure components will first be split into several, with a separation proportional to the square of the field; as the field increases the separations increase, and the components begin to perturb each other in a way which leads ultimately to the ordinary Stark effect.
Foundations of Online Structure Theory II: The Operator Approach
