The Dirac equation in the algebraic approximation. III. Diagrammatic perturbation theory applied to a model problem
H M Quiney; I P Grant; S Wilson; H M Quiney; Dept. of Theor. Chem., Oxford Univ., UK; I P Grant; Dept. of Theor. Chem., Oxford Univ., UK; S Wilson; Dept. of Theor. Chem., Oxford Univ., UK
Журнал:
Journal of Physics B: Atomic and Molecular Physics
Дата:
1985-07-28
Аннотация:
For pt.II see ibid., vol.17, no.7, p.1201 (1984). The solution of the Dirac equation for hydrogen-like atoms within the algebraic approximation, that is, by using finite basis sets, is considered. The model problem of a hydrogenic atom with nuclear charge Z perturbed by a potential-Z'/r is used to demonstrate the feasibility of including relativistic effects in diagrammatic perturbation theory calculations performed within the algebraic approximation. Both ground- and excited state calculations are reported. Particular attention is paid to the choice of basis sets and the handling of the negative-energy states. It is shown that the 'finite basis set disease' can be avoided in perturbation theory calculations by making an appropriate choice of basis sets. Negative-energy states must be included in the perturbation theory summations. The importance of this work to the development of a relativistic many-body perturbation theory of molecular electronic structure is discussed.
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