Canonical statistical adiabatic channel model calculations of the H + CH3 → CH4 recombination reaction on an ab initio potential energy surface. The role of the transitional modes

Abstract

AbstractThe canonical formalism of the statistical adiabatic channel model is used to calculate limiting high pressure rate constants for the H + CH3 → CH4 recombination reaction on a recently reported analytic potential energy surface based on ab initio calculations. An effective adiabatic channel potential which incorporates the Gϕϕ matrix element of the twofold degenerate H3CH transitional bending mode, quartic anharmonicity, and state selected mode coupling effects is implemented. The rate constants calculated over the temperature range 200–1000 K are in very good agreement with recent canonical variational transition state theory calculations performed on the same surface. The comparison with experimental results is also discussed.