Reaction-path analysis of the tunneling splitting in fluxional molecules: Application to the degenerate rearrangement of hydrogen fluoride dimer

Gene C. Hancock, Paul Rejto, Rozeanne Steckler, Franklin B. Brown, David W. Schwenke, Donald G. Truhlar

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29 Scopus citations

Abstract

The small-curvature semiclassical adiabatic (SCSA) approximation, which is based on a reaction-path Hamiltonian, is used to calculate the tunneling splitting due to the degenerate rearrangement of hydrogen fluoride dimer. The calculation employs a semiempirical potential energy surface which approximates the HF molecules as rigid rotators, and for which accurate tunneling splittings have been previously calculated. The semiclassical method is shown to be accurate within 33%. The internal motion of the dimer along the reaction path and the contributions of the generalized normal mode vibrations to reaction-path curvature in the tunneling region are also discussed.

Original languageEnglish (US)
Pages (from-to)4997-5003
Number of pages7
JournalThe Journal of chemical physics
Volume85
Issue number9
DOIs
StatePublished - 1986

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