Development of analytic energy gradient method in nuclear orbital plus molecular orbital theory

Minoru Hoshino, Yasuhiro Tsukamoto, Hiromi Nakai

    Research output: Contribution to journalArticle

    7 Citations (Scopus)

    Abstract

    This study formulates the analytic energy gradients in the Hartree-Fock calculations of the NOMO theory, which simultaneously determines nuclear and electronic wave functions without the Born-Oppenheimer approximation. The formulations correspond to the translation- and rotation-contaminated (TRC), translation-free (TF), and translation- and rotation-free (TRF) treatments. The optimizations of the orbital centers for several diatomic molecules, which have been performed by using the analytic energy gradients, have given the averaged nuclear distances [R0] reflecting the quantum effects of nuclei and the anharmonicity of the potential energy surfaces. The numerical assessments have clarified that the effects of eliminating the translational and rotational contaminations, i.e., the TRF effects are important to improve the evaluations of {R0}, especially for the molecules including hydrogen atoms.

    Original languageEnglish
    Pages (from-to)2575-2585
    Number of pages11
    JournalInternational Journal of Quantum Chemistry
    Volume107
    Issue number14
    DOIs
    Publication statusPublished - 2007 Nov 15

    Fingerprint

    Gradient methods
    Molecular orbitals
    molecular orbitals
    orbitals
    gradients
    Born approximation
    Born-Oppenheimer approximation
    Potential energy surfaces
    Molecules
    Wave functions
    diatomic molecules
    energy
    Hydrogen
    hydrogen atoms
    contamination
    Contamination
    potential energy
    wave functions
    formulations
    Atoms

    Keywords

    • Energy gradient
    • Non-Born-Oppenheimer theory
    • Nuclear orbital plus molecular orbital theory
    • Optimization
    • Vibrational averaging

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Cite this

    Development of analytic energy gradient method in nuclear orbital plus molecular orbital theory. / Hoshino, Minoru; Tsukamoto, Yasuhiro; Nakai, Hiromi.

    In: International Journal of Quantum Chemistry, Vol. 107, No. 14, 15.11.2007, p. 2575-2585.

    Research output: Contribution to journalArticle

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