Description of Core-Ionized and Core-Excited States by Density Functional Theory and Time-Dependent Density Functional Theory

Abstract

This chapter discusses descriptions of core-ionized and core-excited states by density functional theory (DFT) and by time-dependent density functional theory (TDDFT). The core orbitals are analyzed by evaluating core-excitation energies computed by DFT and TDDFT; their orbital energies are found to contain significantly larger self-interaction errors in comparison with those of valence orbitals. The analysis justifies the inclusion of Hartree-Fock exchange (HFx), capable of reducing self-interactions, and motivates construction of hybrid functional with appropriate HFx portions for core and valence orbitals. The determination of the HFx portions based on a first-principle approach is also explored and numerically assessed.