Calculation of high rotation energies of the water molecule using the generating function model

V. G. Tyuterev, V. I. Starikov, S. A. Tashkun, Semen Nikolaevich Mikhaïlenko

    Research output: Contribution to journalArticle

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    Abstract

    The previously developed generating function model is applied in this paper to fitting high rotational levels of the water molecule in the domain of rotational quantum numbers where the standard power series expansion of the rotational Hamiltonian has a slow rate of convergence or even diverges. This model typically provides a considerable improvement in the standard deviation of fit with respect both to the conventional polynomial Hamiltonian and to the Pade-type Hamiltonian (with the same or fewer number of adjustable parameters). Ground state rotational levels recovered by Flaud et al. (Mol. Phys.32, 499-521 (1976)) from flame spectra are fitted with accuracy near that of the experimental values: weighted standard deviation χ = 1.8 for 422 levels up to J, Ka ≤ 20 and χ = 2.1 for all available levels up to J ≤ 35. New ground state data reported by Toth (J. Opt. Soc.B8, 2236-2255 (1991)) are fitted up to J, Ka ≤ 10 with RMS = 4 × 10-5 cm-1. Tests of extrapolation properties of the generating function model are discussed. In certain cases the accuracy of extrapolation was better than the accuracy of fitting with the standard rotational Hamiltonian.

    Original languageEnglish
    Pages (from-to)38-58
    Number of pages21
    JournalJournal of Molecular Spectroscopy
    Volume170
    Issue number1
    DOIs
    Publication statusPublished - 1 Jan 1995

    Fingerprint

    Hamiltonians
    Molecules
    Water
    Extrapolation
    Ground state
    water
    extrapolation
    molecules
    standard deviation
    ground state
    energy
    power series
    series expansion
    quantum numbers
    flames
    polynomials
    Polynomials

    ASJC Scopus subject areas

    • Atomic and Molecular Physics, and Optics
    • Spectroscopy
    • Physical and Theoretical Chemistry

    Cite this

    Calculation of high rotation energies of the water molecule using the generating function model. / Tyuterev, V. G.; Starikov, V. I.; Tashkun, S. A.; Mikhaïlenko, Semen Nikolaevich.

    In: Journal of Molecular Spectroscopy, Vol. 170, No. 1, 01.01.1995, p. 38-58.

    Research output: Contribution to journalArticle

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