Inner-shell excitation of open-shell atoms: a spin-dependent localized Hartree-Fock density-functional approach

摘要

We present a spin-dependent localized Hartree-Fock (SLHF) density-functional approach for the treatment of inner-shell excited states of open-shell atomic systems. In this approach, the electron spin-orbitals and single-Slater-determinant energies of an electronic configuration are computed by solving the Kohn-Sham (KS) equation with SLHF exchange potential. The multiplet energy of an inner-shell excited state is evaluated from the single-Slater-determinant energies in terms of Slater's diagonal sum rule. Based on this procedure, we perform calculations of the total and excitation energies of inner-shell excited states of open-shell atomic systems: Li, B, Ne+, Ne2+, Ne3+ and Na. In the calculation, the electron correlation effect is taken into account via the correlation potential and energy functional of Perdew and Wang (PW) or of Lee, Yang and Parr (LYP). The calculated results are in good agreement with the available experimental and other ab initio theoretical data. In addition, new results for highly excited inner-shell states are also presented.