Transition state theory overestimates reaction rates in solution because conventional dividing surfaces between reagents and products are crossed many times by the same reactive trajectory. We describe a recipe for constructing a time-dependent dividing surface free of such recrossings in the presence of noise. The no-recrossing limit of transition state theory thus becomes generally available for the description of reactions in a fluctuating environment.
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http://dx.doi.org/10.1103/PhysRevLett.95.058301 | DOI Listing |
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