title: Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: core-valence-Rydberg B3LYP.
abstract: The core-valence-Rydberg Becke's three-parameter exchange (B3)+Lee-Yang-Parr (LYP) correlation functional (CVR-B3LYP) is proposed as a means to improve descriptions of Rydberg excitations of core-valence B3LYP (CV-B3LYP). CV-B3LYP describes excitations from both core and occupied valence orbitals to unoccupied valence orbitals with high accuracy but fails to describe those to Rydberg orbitals. CVR-B3LYP, which adopts the appropriate portions of Hartree-Fock exchange for unoccupied valence and Rydberg regions separately, overcomes the disadvantage of CV-B3LYP. Numerical assessment confirms that time-dependent density functional theory calculations with CVR-B3LYP succeed in describing not only core excitations but also Rydberg excitations 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: Hiromi
authors.initials: H
authors.lastname: Nakai