Time-dependent density functional theory calculations for core-excited states: Assessment of standard exchange-correlation functionals and development of a novel hybrid functional

Ayako Nakata, Yutaka Imamura, Takao Otsuka, Hiromi Nakai

Research output: Contribution to journalArticle

57 Citations (Scopus)

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.

Original languageEnglish
Article number094105
JournalJournal of Chemical Physics
Volume124
Issue number9
DOIs
Publication statusPublished - 2006 Mar 13

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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