Inner-electron rearrangement in the Hartree-Fock scheme

Abstract

Atomic self-consistent field calculations are performed by numerical solution of the Hartree-Fock equations on each of the atoms in the third row of the periodic system, both with all the valence electrons present and with all the valence electrons absent. Ionization energies resulting when the inner shells are not allowed to relax, as well as the contributions to the ionization energies from the relaxation of the inner shells, are evaluated along that series for the first time, and are separately examined: contributions shown by the 1s, 2s and 2p orbitals upon stripping off of the valence electrons are not all of the same sign. The same is true of the changes in the mean radii of these orbitals. These results are explained in terms of exchange and Coulomb interactions between inner and valence (outer) shells, and as a consequence of the variations in the nuclear screening. The accuracy of Koopmans' theorem for monovalent species is tested by comparison with the Hartree-Fock contribution to the ionization potential of the valence electron. Hartree-Fock and experimental ionization potentials are also compared along the above-mentioned series of third-row elements.