The semiclassical self-consistent-field (SC-SCF) approach to energy levels of coupled vibrational modes. II. The semiclassical state-interaction procedure

Mark A Ratner, V. Buch, R. B. Gerber

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Abstract

A method for obtaining energy levels of coupled vibrational modes is described, that utilizes a state-interaction approach combined with semiclassical approximations. The method starts with a semiclassical self-consistent-field calculation of the coupled problem, and uses the eigenstates of the resulting Hartree-like separable SCF vibrational hamiltonian to define a basis set of Hartree products in which the full vibrational hamiltonian is represented and diagonalized. Matrix elements of any interaction potential between single-mode states are approximated semiclassically as the Fourier component of the interaction at the frequency corresponding to the SCF eigenvalue difference. A Fourier-component expression can also be given for the overlap between non-orthogonal single mode states. Thus no wavefunctions ever need to be defined. Application to a sample two-mode problem shows that the method is highly accurate. Further possible applications, in particular to intramolecular rate calculations are noted.

Original languageEnglish
Pages (from-to)345-356
Number of pages12
JournalChemical Physics
Volume53
Issue number3
DOIs
Publication statusPublished - Dec 1 1980

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ASJC Scopus subject areas

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

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