Multipole Polarizabilities from Hartree-Fock Densities by Statistical Perturbation Theory, a Semiempirical Approach

Abstract

Abstract A statistical variation-perturbation method is used in the derivation of multipole polarizabilities from Hartree-Fock electron densities. A quantum correction of the kinetic energy expressions takes into account the exponential decrease of the electron density in the outer part of the atom. The method is called semiempirical because of the still unsolved problem of the kinetic energy in the statistical theory of the atom. The results are compared to the best available experimental and theoretical values of dipole-and quadrupole-polarizabilities and show agreement within approxi-mately 10 - 15 percent. They are lower than Hartree-Fock perturbation results. As the numerical calculations are reduced to single integrations, the mathematical labor is considerably reduced. In an appendix dipole polarizabilities are calculated in the framework of the Gombas model including exchange and correlation for ionization degrees from zero to six.