Comparative study of potential energy surfaces for CH/sub 3/+H/sub 2/bold-arrow-left-rightCH/sub 4/+H

Journal Article · Tue Dec 15 04:00:00 EST 1987 · J. Chem. Phys.; (United States)

OSTI ID:5976211

Steckler, R; Dykema, K J; Brown, F B; Hancock, G C; Truhlar, D G; Valencich, T

We analyze potential energy surfaces that have been proposed by one of the authors, Bunker, and Chapman and by Raff for the reaction CH/sub 3/+H/sub 2/bold-arrow-left-rightCH/sub 4/+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.

• Research Organization: Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
• OSTI ID: 5976211
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 87:12; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYL RADICALS
CHEMICAL REACTION KINETICS
ELEMENTS
ENERGY
HYDROGEN
KINETICS
METHYL RADICALS
NONMETALS
POTENTIAL ENERGY
RADICALS
REACTION KINETICS