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Updated: Mar 17, 2026
Unraveling Entropic Rate Acceleration Induced by Solvent Dynamics in Membrane Enzymes
Published on: January 16, 2016
Transition state theory for solvated reactions beyond recrossing-free dividing surfaces
F Revuelta1,2, Thomas Bartsch3, P L Garcia-Muller4
1Grupo de Sistemas Complejos, Escuela Técnica Superior de Ingeniería Agronómica, Alimentaria y de Biosistemas, Universidad Politécnica de Madrid, Avda. Complutense s/n 28040 Madrid, Spain.
Abstract:
The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing-free dividing surface. We show here that it is possible to define such optimal dividing surface in systems with non-Markovian friction. However, a more direct approach to rate calculation is based on invariant manifolds and avoids the use of a dividing surface altogether, Using that method we obtain an explicit expression for the rate of crossing an anharmonic potential barrier. The excellent performance of our method is illustrated with an application to a realistic model for LiNC⇌LiCN isomerization.
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