Is the divide-and-conquer Hartree-Fock method valid for calculations of delocalized systems?

Tomoko Akama, Atsuhiko Fujii, Masato Kobayashi, Hiromi Nakai

    Research output: Contribution to journalArticle

    37 Citations (Scopus)

    Abstract

    Recently, we applied Yang's divide-and-conquer (DC) method to the Hartree-Fock (HF) and hybrid density functional theories and assessed its reliability in calculations of bond-alternating polyene chains. In this paper, we investigate the cut-off behaviour of the HF exchange interaction in the DC-HF method by comparing the results of bond-alternating polyene chains with those of more delocalized uniform polyene chains. The cut-off error of the uniform chain is much larger than that of the bond-alternating chain because of the delocalized electronic structure of the uniform polyene chain. We also estimate the exponential decay coefficient of the cut-off error in the DC scheme and compare it with that of the real-space one-particle density matrix, which can be represented by the band gap in the insulator limit. It can be concluded that the cut-off derived from the DC-HF method can be reduced to an arbitrary magnitude of error by adopting an appropriate buffer radius corresponding to the band gap.

    Original languageEnglish
    Pages (from-to)2799-2804
    Number of pages6
    JournalMolecular Physics
    Volume105
    Issue number19-22
    DOIs
    Publication statusPublished - 2007 Oct 21

    Fingerprint

    Polyenes
    cut-off
    Energy gap
    Exchange interactions
    Electronic structure
    Density functional theory
    Buffers
    buffers
    insulators
    density functional theory
    electronic structure
    radii
    decay
    coefficients
    estimates

    Keywords

    • Delocalized system
    • Divide-and-conqure method
    • Hartree-Fock exchange
    • Linear-scaling method

    ASJC Scopus subject areas

    • Atomic and Molecular Physics, and Optics

    Cite this

    Is the divide-and-conquer Hartree-Fock method valid for calculations of delocalized systems? / Akama, Tomoko; Fujii, Atsuhiko; Kobayashi, Masato; Nakai, Hiromi.

    In: Molecular Physics, Vol. 105, No. 19-22, 21.10.2007, p. 2799-2804.

    Research output: Contribution to journalArticle

    Akama, Tomoko ; Fujii, Atsuhiko ; Kobayashi, Masato ; Nakai, Hiromi. / Is the divide-and-conquer Hartree-Fock method valid for calculations of delocalized systems?. In: Molecular Physics. 2007 ; Vol. 105, No. 19-22. pp. 2799-2804.
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