Relativistic Calculations of Electron Binding Energies by a Modified Hartree-Fock-Slater Method

Abstract

Relativistic atomic wave functions and electron binding energies have been calculated by a modified Hartree-Fock-Slater method. The local exchange approximation, originally introduced by Slater, is modified in such a way that the total energy of the system is minimized. Approximate expressions for the optimum exchange potential are suggested for all atoms and ions. The total atomic energies and electron binding energies obtained by this method agree extremely well with the corresponding Hartree-Fock results in the cases where such data are available. Various corrections to the theoretical binding energies are discussed, in particular the effect of rearrangement during the ionization process. It is found that this effect is of importance for inner shells in all elements and is responsible for the main discrepancy between experimental and previous theoretical results for light and medium-heavy elements. For heavy elements other effects are of importance, and various possible sources of the residual discrepancy between theory and experiments are discussed.