Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-valence-Rydberg B3LYP

Ayako Nakata, Yutaka Imamura, Hiromi Nakai

    Research output: Contribution to journalArticle

    52 Citations (Scopus)

    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.

    Original languageEnglish
    Article number064109
    JournalJournal of Chemical Physics
    Volume125
    Issue number6
    DOIs
    Publication statusPublished - 2006

    Fingerprint

    Density functional theory
    valence
    excitation
    orbitals
    density functional theory

    ASJC Scopus subject areas

    • Atomic and Molecular Physics, and Optics

    Cite this

    Hybrid exchange-correlation functional for core, valence, and Rydberg excitations : Core-valence-Rydberg B3LYP. / Nakata, Ayako; Imamura, Yutaka; Nakai, Hiromi.

    In: Journal of Chemical Physics, Vol. 125, No. 6, 064109, 2006.

    Research output: Contribution to journalArticle

    @article{fe7d61e8597c41f4bdbaa0a39937b686,
    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.",
    author = "Ayako Nakata and Yutaka Imamura and Hiromi Nakai",
    year = "2006",
    doi = "10.1063/1.2227379",
    language = "English",
    volume = "125",
    journal = "Journal of Chemical Physics",
    issn = "0021-9606",
    publisher = "American Institute of Physics Publising LLC",
    number = "6",

    }

    TY - JOUR

    T1 - Hybrid exchange-correlation functional for core, valence, and Rydberg excitations

    T2 - Core-valence-Rydberg B3LYP

    AU - Nakata, Ayako

    AU - Imamura, Yutaka

    AU - Nakai, Hiromi

    PY - 2006

    Y1 - 2006

    N2 - 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.

    AB - 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.

    UR - http://www.scopus.com/inward/record.url?scp=33747314443&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=33747314443&partnerID=8YFLogxK

    U2 - 10.1063/1.2227379

    DO - 10.1063/1.2227379

    M3 - Article

    AN - SCOPUS:33747314443

    VL - 125

    JO - Journal of Chemical Physics

    JF - Journal of Chemical Physics

    SN - 0021-9606

    IS - 6

    M1 - 064109

    ER -