title: Time-dependent density functional theory calculations for core-excited states: assessment of standard exchange-correlation functionals and development of a novel hybrid functional.
abstract: A new hybrid functional for accurate descriptions of core and valence excitations, the core-valence Becke's three-parameter exchange (B3)+Lee-Yang-Paar (LYP) correlation functional (CV-B3LYP), is proposed. The construction of the new hybrid functional is based on the assessment that B3LYP performs well for properties concerning valence electrons and Becke's half-and-half exchange+LYP functional (BHHLYP), which includes 50% portion of Hartree-Fock exchange, performs well for core excitations. By using the appropriate portions of Hartree-Fock exchange for core and valence regions separately, CV-B3LYP overcomes the disadvantages of BHHLYP and B3LYP, which give inferior descriptions of valence and core excitations, respectively. Density functional theory (DFT) calculations with the CV-B3LYP functional reproduce core- and valence-orbital energies close to those of BHHLYP and B3LYP, respectively. Time-dependent DFT calculations with the CV-B3LYP functional yield both core- and valence-excitation energies with reasonable accuracy.
authors.affiliation: Department of Chemistry, School of Science and Engineering, Waseda University, Tokyo 169-8555, Japan.
authors.forename: Ayako
authors.initials: A
authors.lastname: Nakata
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Imamura
authors.forename: Takao
authors.initials: T
authors.lastname: Otsuka
authors.forename: Hiromi
authors.initials: H
authors.lastname: Nakai