Title

Thermal Rate Constants for H + CH3  CH4 Recombination. II. Comparison of Experiment and Canonical Variational Transition State Theory

Document Type

Article

Publication Date

5-1987

Publication Source

Journal of American Chemical Society

Volume

109

Issue

10

Inclusive pages

2916–2922

DOI

10.1021/ja00244a010

Abstract

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.

Disciplines

Chemistry