Generalized Møller-Plesset partitioning in multiconfiguration perturbation theory

Masato Kobayashi, Ágnes Szabados, Hiromi Nakai, Péter R. Surján

    Research output: Contribution to journalArticle

    35 Citations (Scopus)

    Abstract

    Two perturbation (PT) theories are developed starting from a multiconfiguration (MC) zero-order function. To span the configuration space, the theories employ biorthogonal vector sets introduced in the MCPT framework. At odds with previous formulations, the present construction operates with the full Fockian corresponding to a principal determinant, giving rise to a nondiagonal matrix of the zero-order resolvent. The theories provide a simple, generalized Møller-Plesset (MP) second-order correction to improve any reference function, corresponding either to a complete or incomplete model space. Computational demand of the procedure is determined by the iterative inversion of the Fockian, similarly to the single reference MP theory calculated in a localized basis. Relation of the theory to existing multireference (MR) PT formalisms is discussed. The performance of the present theories is assessed by adopting the antisymmetric product of strongly orthogonal geminal (APSG) wave functions as the reference function.

    Original languageEnglish
    Pages (from-to)2024-2033
    Number of pages10
    JournalJournal of Chemical Theory and Computation
    Volume6
    Issue number7
    DOIs
    Publication statusPublished - 2010 Jul 13

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    perturbation theory
    Orthogonal functions
    Wave functions
    determinants
    wave functions
    inversions
    formulations
    perturbation
    products
    matrices
    configurations
    S-(N-monomethoxytritylaminoethyl)-O-(2-chlorophenyl)phosphorothioate

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Computer Science Applications

    Cite this

    Generalized Møller-Plesset partitioning in multiconfiguration perturbation theory. / Kobayashi, Masato; Szabados, Ágnes; Nakai, Hiromi; Surján, Péter R.

    In: Journal of Chemical Theory and Computation, Vol. 6, No. 7, 13.07.2010, p. 2024-2033.

    Research output: Contribution to journalArticle

    Kobayashi, Masato ; Szabados, Ágnes ; Nakai, Hiromi ; Surján, Péter R. / Generalized Møller-Plesset partitioning in multiconfiguration perturbation theory. In: Journal of Chemical Theory and Computation. 2010 ; Vol. 6, No. 7. pp. 2024-2033.
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