One-body energy decomposition schemes revisited: Assessment of mulliken-, grid-, and conventional energy density analyses

Yasuaki Kikuchi, Yutaka Imamura, Hiromi Nakai

    Research output: Contribution to journalArticle

    5 Citations (Scopus)

    Abstract

    We propose a new energy density analysis (EDA) that evaluates atomic contributions of all energy terms, i.e., the kinetic, nuclear-attraction, Coulomb, and Hartree-Fock (HF) exchange and density functional theory (DFT) exchange-correlation energies using the Mulliken-type partitioning. Although widely used DFT exchangecorrelation functionals are nonlinear expressions in terms of density, they are decomposed into atomic contributions by focusing the linear part of the density. Numerical assessment on Mulliken-EDA, Grid-EDA, and conventional EDA has been carried out for the G2-1 set. Correlations between HF and DFT exchanges demonstrate that a consistent partitioning of all energy terms is essential for EDA. These numerical results confirm that the present Mulliken-EDA offers a more reasonable picture for the atomization process.

    Original languageEnglish
    Pages (from-to)2464-2473
    Number of pages10
    JournalInternational Journal of Quantum Chemistry
    Volume109
    Issue number11
    DOIs
    Publication statusPublished - 2009

    Fingerprint

    Density functional theory
    flux density
    grids
    Decomposition
    decomposition
    Atomization
    density functional theory
    energy
    Kinetics
    atomizing
    functionals
    attraction
    kinetics

    Keywords

    • Becke's partitioning function
    • Density functional theory
    • Energy density analysis
    • Grid-EDA
    • Mulliken population analysis

    ASJC Scopus subject areas

    • Condensed Matter Physics
    • Atomic and Molecular Physics, and Optics
    • Physical and Theoretical Chemistry

    Cite this

    One-body energy decomposition schemes revisited : Assessment of mulliken-, grid-, and conventional energy density analyses. / Kikuchi, Yasuaki; Imamura, Yutaka; Nakai, Hiromi.

    In: International Journal of Quantum Chemistry, Vol. 109, No. 11, 2009, p. 2464-2473.

    Research output: Contribution to journalArticle

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