Fractional power dependence of rate on activation energy for reactions with very low internal barriers

The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate, k I, are obtained by solving the associated first passage time problems. Both the average rate constant, k I, and the numerically calcu...

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Bibliographic Details
Published in:Chemical physics letters 1988-08, Vol.149 (4), p.411-416
Main Authors: Poornimadevi, C.S., Bagchi, Biman
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
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Summary:The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate, k I, are obtained by solving the associated first passage time problems. Both the average rate constant, k I, and the numerically calculated long-time rate constant, k L, show a fractional power law dependence on the barrier height for very low barriers. The crossover of the reaction dynamics from low to high barrier is investigated.
ISSN:0009-2614
1873-4448
DOI:10.1016/0009-2614(88)85116-9