A comparative study of potential energy surfaces for CH3+H 2↔CH4+H

Rozeanne Steckler, Kenneth J. Dykema, Franklin B. Brown, Gene C. Hancock, Donald G. Truhlar, Trina Valencich

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61 Scopus citations

Abstract

We analyze potential energy surfaces that have been proposed by one of the authors, Bunker, and Chapman and by Raff for the reaction CH3 + H2↔CH4 + H. The surfaces are modified to remove discontinuities and zero frequencies, where present, and the modified surfaces are compared to each other in terms of reaction-path properties and to ab initio calculations for stationary point properties. They are also used for rate constant calculations which are compared to experiment. The rate constants were calculated by improved canonical variational transition state theory with small-curvature semiclassical adiabatic ground-state transmission coefficients (ICVT/SCSAG) over a wide temperature range, 298-1340 K. Both surfaces yield rate constants in poor agreement with experimental values. The reaction-path analysis leads to a list of potential energy surface features that are important for the rate constants but inaccurate in the existing surfaces and that should be improved in subsequent work.

Original languageEnglish (US)
Pages (from-to)7024-7035
Number of pages12
JournalThe Journal of chemical physics
Volume87
Issue number12
DOIs
StatePublished - 1987

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