The influence of intramolecular vibrational relaxation on the pressure dependence of unimolecular rate constants
- 1 July 1986
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 85 (1) , 146-149
- https://doi.org/10.1063/1.451651
Abstract
We study the rate constant in a bistable two degree of freedom system subject to impulsive BGK collisions. We find that the rate constant is very sensitive to the coupling of the degrees of freedom in the low collision regime. RRKM theory often overestimates the low collision rise—especially at higher collision rates, where the rate constant rises much more slowly making the molecule appear to have fewer degrees of freedom. We argue that such effects should be seen in experiments extending over a very wide range of pressures.Keywords
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