Abstract
An exact expression for the spin-orbit coupling constant is derived within the Hartree-Fock description of the atom by considering the two body mutual spin-orbit interaction between electrons. The interaction is rewritten in tensor operator form and the contribution of outer electron-core interactions to the coupling constant is calculated. We find that the usual expression <
3F/r8r
> where
V
is the Hartree potential is only approximate, and that certain exchange type terms, which arise because we are dealing with a two-body interaction and determinantal wave function, must also be included. These exchange terms are not simply related to the ordinary electrostatic exchange. The resulting expression for the spin-orbit coupling constant is given in terms of radial integrals which can be calculated using Hartree or Hartree—Fock wave functions. We also discuss the effective magnetic Hamiltonian to be used for the calculation of matrix elements within an atomic configuration.
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