Thermal Rate Constants for H + CH3 CH4 Recombination. II. Comparison of Experiment and Canonical Variational Transition State Theory
Journal of American Chemical Society
Canonical variational transition state theory is used to calculate bimolecular rate constants for H + CH, and D + CH, recombination. The calculations are performed on an analytic potential energy surface derived from recent ab initio calculations. Rate constants calculated for this surface are in very good agreement with the experimental values. The H(D)- - -CH3 transitional rocking modes are treated as quantum harmonic oscillators or classical hindered rotors in the calculations. These two treatments give rate constants which agree to within 15%. The variational transition states become tighter as the temperature is increased.
W L. Hase, S L. Mondro, Ronald J. Duchovic, and D M. Hirst (1987).
Thermal Rate Constants for H + CH3 CH4 Recombination. II. Comparison of Experiment and Canonical Variational Transition State Theory. Journal of American Chemical Society.109 (10), 2916–2922.