Grid-based energy density analysis

Implementation and assessment

Yutaka Imamura, Asuka Takahashi, Hiromi Nakai

    Research output: Contribution to journalArticle

    21 Citations (Scopus)

    Abstract

    Grid-based energy density analysis (grid-EDA) that decomposes the total energy into atomic energies by a space-partitioning function is proposed. The kinetic energy, nuclear attraction, and exchange-correlation functional are evaluated on grid points and are split into atomic contributions. To reduce numerical errors in the conventional scheme of numerical integration, the electronic Coulomb and HF exchange interactions are evaluated by the pseudospectral method, which was first applied to an ab initio method by Friesner [Chem. Phys. Lett. 116, 39 (1985)], and are decomposed into atomic contributions. Grid-EDA using the pseudospectral method succeeds in ensuring less than 1 kcalmol error in total energies for small molecules and providing reliable atomic energy contributions for the problematic lithium cluster, which exhibits a strong basis-set dependence for Mulliken-type EDA. Also, site-dependent atomization energies are estimated by grid-EDA for cluster models such as Li48, C41 H60, and Mg32 O32. Grid-EDA reveals that these models imitate crystal environments reasonably because atomization energies estimated from the inner atoms of the models are close to the experimental cohesive energies.

    Original languageEnglish
    Article number034103
    JournalJournal of Chemical Physics
    Volume126
    Issue number3
    DOIs
    Publication statusPublished - 2007

    Fingerprint

    flux density
    grids
    Atomization
    Nuclear energy
    atomizing
    nuclear energy
    Exchange interactions
    Lithium
    Kinetic energy
    energy
    function space
    Atoms
    Crystals
    Molecules
    numerical integration
    attraction
    lithium
    kinetic energy
    electronics
    crystals

    ASJC Scopus subject areas

    • Atomic and Molecular Physics, and Optics

    Cite this

    Grid-based energy density analysis : Implementation and assessment. / Imamura, Yutaka; Takahashi, Asuka; Nakai, Hiromi.

    In: Journal of Chemical Physics, Vol. 126, No. 3, 034103, 2007.

    Research output: Contribution to journalArticle

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