Abstract
Canonical variational transition state theory is used to calculate bimolecular rate constants for H + CH3and D + CH3recombination. 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)- - -CH3transitional 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.
Original language | English |
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Pages (from-to) | 2916-2922 |
Number of pages | 7 |
Journal | Journal of the American Chemical Society |
Volume | 109 |
Issue number | 10 |
DOIs | |
State | Published - May 1 1987 |