A modified variation-perturbation approach to zero-point vibrational motion

Per-Olof Åstrand, K. Ruud, D. Sundholm

    Research output: Contribution to journalJournal articleResearchpeer-review

    Abstract

    We present a detailed investigation of the perturbation approach for calculating zero-point vibrational contributions to molecular properties. It is demonstrated that if the sum of the potential energy and the zero-point vibrational energy is regarded as an effective potential energy, the leading contribution to the first-order wave function vanishes in the perturbation approach. Two different perturbation approaches have been investigated numerically by calculations of some magnetic properties for a few diatomic molecules and the results obtained have been compared to the exact numerical results. It is shown that only a few terms need to be included in a perturbation expansion to obtain an accuracy in the calculated rovibrational contribution better than the quality normally obtained for the potential and property surfaces in electronic structure calculations.
    Original languageEnglish
    JournalTheoretical Chemistry Accounts
    Volume103
    Issue number5
    Pages (from-to)365-373
    ISSN1432-881X
    DOIs
    Publication statusPublished - 2000

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