Deuterium and carbon-13 kinetic isotope effects for the reaction of OH with CH[sub 4]
- Department of Chemistry and Supercomputer Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431 (United States)
Interpolated variational transition state theory calculations with centrifugal-dominant, small-curvature tunneling coefficients have been carried out for the case of the deuterium kinetic isotope effect (KIE) in the reaction OH+[sup 12]CD[sub 4][r arrow]HDO+[sup 12]CD[sub 3] and for the [sup 13]C KIE for the reaction OH+[sup 13]CH[sub 4][r arrow]H[sub 2]O+[sup 13]CH[sub 3]. The interpolated variationally optimized generalized transition states predict notably different nontunneling KIEs than the conventional ones, and factorization analyses of the KIEs are presented to illustrate the origin of the differences. The zero-point energies at the variational transition states differ from those at the saddle point by up to 0.19 kcal/mol for the OH+[sup 12]CD[sub 4] reaction and by up to 0.34 kcal/mol for the OH+[sup 13]CH[sub 4] reaction. The incorporation of multidimensional tunneling effects partly cancels the effect of variational optimization of the transition state.
- DOE Contract Number:
- FG02-86ER13579
- OSTI ID:
- 6236795
- Journal Information:
- Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 99:5; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKANES
CALCULATION METHODS
CARBON 12
CARBON 13
CARBON ISOTOPES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DEUTERIUM
ELEMENTS
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
HYDROCARBONS
HYDROGEN
HYDROGEN ISOTOPES
HYDROXYL RADICALS
INTERPOLATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
METHANE
NONMETALS
NUCLEI
NUMERICAL SOLUTION
ODD-ODD NUCLEI
OPTIMIZATION
ORGANIC COMPOUNDS
RADICALS
REACTION KINETICS
STABLE ISOTOPES
TUNNEL EFFECT
VARIATIONAL METHODS