Transition state in a noisy environment

Phys Rev Lett. 2005 Jul 29;95(5):058301. doi: 10.1103/PhysRevLett.95.058301. Epub 2005 Jul 25.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Algorithms*
  • Computer Simulation
  • Models, Chemical*
  • Nonlinear Dynamics*
  • Oscillometry / methods*
  • Stochastic Processes*