Description of core excitations by time-dependent density functional theory with local density approximation, generalized gradient approximation, meta-generalized gradient approximation, and hybrid functionals

Yutaka Imamura, Takao Otsuka, Hiromi Nakai

    Research output: Contribution to journalArticle

    30 Citations (Scopus)

    Abstract

    Time-dependent density functional theory (TDDFT) is employed to investigate exchange-correlation-functional dependence of the vertical core-excitation energies of several molecules including H, C, N, O, and F atoms. For the local density approximation (LDA), generalized gradient approximation (GGA), and meta-GGA, the calculated Xls-π* excitation energies (X = C, N, O, and F) are severely underestimated by more than 13 eV. On the other hand, time-dependent Hartree-Fock (TDHF) overestimates the excitation energies by more than 6 eV. The hybrid functionals perform better than pure TDDFT because HF exchange remedies the underestimation of pure TDDFT. Among these hybrid functionals, the Becke-Half-and-Half-Lee-Yang-Parr (BHHLYP) functional including 50% HF exchange provides the smallest error for core excitations. We have also discovered the systematic trend that the deviations of TDHF and TDDFT with the LDA, GGA, and meta-GGA functionals show a strong atomdependence. Namely, their deviations become larger for heavier atoms, while the hybrid functionals are significantly less atom-dependent.

    Original languageEnglish
    Pages (from-to)2067-2074
    Number of pages8
    JournalJournal of Computational Chemistry
    Volume28
    Issue number12
    DOIs
    Publication statusPublished - 2007 Sep

    Fingerprint

    Time-dependent Density Functional Theory
    Local density approximation
    Generalized Gradient
    Density functional theory
    Excitation energy
    Excitation
    Approximation
    Atoms
    Energy
    Large Deviations
    Molecules
    Deviation
    Vertical
    Dependent

    Keywords

    • Atom-dependence
    • Core excitations
    • Functional-dependence
    • Time-dependent density functional theory

    ASJC Scopus subject areas

    • Chemistry(all)
    • Safety, Risk, Reliability and Quality

    Cite this

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    title = "Description of core excitations by time-dependent density functional theory with local density approximation, generalized gradient approximation, meta-generalized gradient approximation, and hybrid functionals",
    abstract = "Time-dependent density functional theory (TDDFT) is employed to investigate exchange-correlation-functional dependence of the vertical core-excitation energies of several molecules including H, C, N, O, and F atoms. For the local density approximation (LDA), generalized gradient approximation (GGA), and meta-GGA, the calculated Xls-π* excitation energies (X = C, N, O, and F) are severely underestimated by more than 13 eV. On the other hand, time-dependent Hartree-Fock (TDHF) overestimates the excitation energies by more than 6 eV. The hybrid functionals perform better than pure TDDFT because HF exchange remedies the underestimation of pure TDDFT. Among these hybrid functionals, the Becke-Half-and-Half-Lee-Yang-Parr (BHHLYP) functional including 50{\%} HF exchange provides the smallest error for core excitations. We have also discovered the systematic trend that the deviations of TDHF and TDDFT with the LDA, GGA, and meta-GGA functionals show a strong atomdependence. Namely, their deviations become larger for heavier atoms, while the hybrid functionals are significantly less atom-dependent.",
    keywords = "Atom-dependence, Core excitations, Functional-dependence, Time-dependent density functional theory",
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    T1 - Description of core excitations by time-dependent density functional theory with local density approximation, generalized gradient approximation, meta-generalized gradient approximation, and hybrid functionals

    AU - Imamura, Yutaka

    AU - Otsuka, Takao

    AU - Nakai, Hiromi

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    N2 - Time-dependent density functional theory (TDDFT) is employed to investigate exchange-correlation-functional dependence of the vertical core-excitation energies of several molecules including H, C, N, O, and F atoms. For the local density approximation (LDA), generalized gradient approximation (GGA), and meta-GGA, the calculated Xls-π* excitation energies (X = C, N, O, and F) are severely underestimated by more than 13 eV. On the other hand, time-dependent Hartree-Fock (TDHF) overestimates the excitation energies by more than 6 eV. The hybrid functionals perform better than pure TDDFT because HF exchange remedies the underestimation of pure TDDFT. Among these hybrid functionals, the Becke-Half-and-Half-Lee-Yang-Parr (BHHLYP) functional including 50% HF exchange provides the smallest error for core excitations. We have also discovered the systematic trend that the deviations of TDHF and TDDFT with the LDA, GGA, and meta-GGA functionals show a strong atomdependence. Namely, their deviations become larger for heavier atoms, while the hybrid functionals are significantly less atom-dependent.

    AB - Time-dependent density functional theory (TDDFT) is employed to investigate exchange-correlation-functional dependence of the vertical core-excitation energies of several molecules including H, C, N, O, and F atoms. For the local density approximation (LDA), generalized gradient approximation (GGA), and meta-GGA, the calculated Xls-π* excitation energies (X = C, N, O, and F) are severely underestimated by more than 13 eV. On the other hand, time-dependent Hartree-Fock (TDHF) overestimates the excitation energies by more than 6 eV. The hybrid functionals perform better than pure TDDFT because HF exchange remedies the underestimation of pure TDDFT. Among these hybrid functionals, the Becke-Half-and-Half-Lee-Yang-Parr (BHHLYP) functional including 50% HF exchange provides the smallest error for core excitations. We have also discovered the systematic trend that the deviations of TDHF and TDDFT with the LDA, GGA, and meta-GGA functionals show a strong atomdependence. Namely, their deviations become larger for heavier atoms, while the hybrid functionals are significantly less atom-dependent.

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    KW - Core excitations

    KW - Functional-dependence

    KW - Time-dependent density functional theory

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