Spin-dependent localized Hartree-Fock density-functional approach for the accurate treatment of inner-shell excitation of close-shell atoms

Abstract

We present a spin-dependent localized Hartree-Fock (SLHF) density-functional approach for the treatment of the inner-shell excited-state calculation of atomic systems. In this approach, the electron spin-orbitals in an electronic configuration are obtained first by solving Kohn-Sham (KS) equation with SLHF exchange potential. Then a single-Slater-determinant energy of the electronic configuration is calculated by using these electron spin-orbitals. Finally, a multiplet energy of an inner-shell excited state is evaluated from the single-Slater-determinant energies of the electronic configurations involved in terms of Slater's diagonal sum rule. This procedure has been used to calculate the total and excitation energies of inner-shell excited states of close-shell atomic systems: Be, B^+, Ne, and Mg. The correlation effect is taken into account by incorporating the correlation potentials and energy functionals of Perdew and Wang's (PW) or Lee, Yang, and Parr's (LYP) into calculation. The calculated results with the PW and LYP energy functionals are in overall good agreement with each other and also with available experimental and other ab initio theoretical data. In addition, we present some new results for highly excited inner-shell states.