Hartree-Fock-Roothaan wave functions, electron density distribution, diamagnetic susceptibility, dipole polarizability and antishielding factor for ions in crystals

Abstract

Using the Hartree-Fock method the wave functions of Li+, Be2+, O2−, F−, Na+, Mg2+, Al3+, S2−, Cl−, K+, Ca2+, Sc3+ and Ti4+ have been calculated for the free ion and the ion in a potential well. The main result of these calculations is a contraction of the anion and an expansion of the cation due to the external potential. A comparison of the calculations with an experimental determination of the electron density distribution in NaCl and MgO shows qualitative agreement. The diamagnetic susceptibility χ, the dipole polarizability αd, and the Sternheimer antishielding factor γ∞ of the ions given above were also calculated for the free ions and the “spherical potential” ions (SPI). The charged hollow sphere model improves the theoretical values towards the properties determined by experiment.