Deuterium and carbon-13 kinetic isotope effects for the reaction of OH with CH4

Abstract

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+12CD4→HDO+12CD3 and for the 13C KIE for the reaction OH+13CH4→H2O+13CH3. 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+12CD4 reaction and by up to 0.34 kcal/mol for the OH+13CH4 reaction. The incorporation of multidimensional tunneling effects partly cancels the effect of variational optimization of the transition state.