Extension of the core-valence-Rydberg B3LYP functional to core-excited-state calculations of third-row atoms

Ayako Nakata, Yutaka Imamura, Hiromi Nakai

    Research output: Contribution to journalArticle

    33 Citations (Scopus)

    Abstract

    A modified core-valence-Rydberg Becke's three-parameter exchange (B3) + Lee-Yang-Parr (LYP) correlation (CVR-B3LYP) functional is proposed in order to calculate core-excitation energies of third-row atoms with reasonable accuracy. The assessment of conventional exchange-correlation functionals shows that the appropriate portions of Hartree-Fock (HF) exchange for core-excited-state calculations depend on shells: 70% and 50% for K-shell and L-shell excitations, respectively. Therefore, the modified CVR-B3LYP functional is designed to use the appropriate portions of HF exchange, 70%, 50%, and 20%, for K-shell, L-shell, and valence regions separately. Time-dependent density functional theory calculations with the modified CVR-B3LYP functional yield both K-shell and L-shell excitation energies with reasonable accuracy. The modified CVR-B3LYP also provides valence-excitation energies and standard enthalpies of formation accurately. Thus, the modified CVR-B3LYP describes all of the K-shell, L-shell, and valence electrons appropriately.

    Original languageEnglish
    Pages (from-to)1295-1305
    Number of pages11
    JournalJournal of Chemical Theory and Computation
    Volume3
    Issue number4
    DOIs
    Publication statusPublished - 2007 Jul

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    Excitation energy
    Excited states
    valence
    Atoms
    excitation
    atoms
    Density functional theory
    Enthalpy
    Electrons
    functionals
    energy
    enthalpy
    density functional theory
    electrons

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Computer Science Applications

    Cite this

    Extension of the core-valence-Rydberg B3LYP functional to core-excited-state calculations of third-row atoms. / Nakata, Ayako; Imamura, Yutaka; Nakai, Hiromi.

    In: Journal of Chemical Theory and Computation, Vol. 3, No. 4, 07.2007, p. 1295-1305.

    Research output: Contribution to journalArticle

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    abstract = "A modified core-valence-Rydberg Becke's three-parameter exchange (B3) + Lee-Yang-Parr (LYP) correlation (CVR-B3LYP) functional is proposed in order to calculate core-excitation energies of third-row atoms with reasonable accuracy. The assessment of conventional exchange-correlation functionals shows that the appropriate portions of Hartree-Fock (HF) exchange for core-excited-state calculations depend on shells: 70{\%} and 50{\%} for K-shell and L-shell excitations, respectively. Therefore, the modified CVR-B3LYP functional is designed to use the appropriate portions of HF exchange, 70{\%}, 50{\%}, and 20{\%}, for K-shell, L-shell, and valence regions separately. Time-dependent density functional theory calculations with the modified CVR-B3LYP functional yield both K-shell and L-shell excitation energies with reasonable accuracy. The modified CVR-B3LYP also provides valence-excitation energies and standard enthalpies of formation accurately. Thus, the modified CVR-B3LYP describes all of the K-shell, L-shell, and valence electrons appropriately.",
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