Transition State Theory for solvated reactions beyond recrossing-free dividing surfaces
arXiv:1605.03339 · doi:10.1103/PhysRevE.93.062304
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 LiNCLiCN isomerization.
arXiv comment5 pages, 3 figures, 1 table
References in corpus (11)
- The Transition State in a Noisy Environment
- Stochastic Transition States: Reaction Geometry amidst Noise
- A Computational Procedure to Detect a New Type of High Dimensional Chaotic Saddle and its Application to the 3-D Hill's Problem
- Identifying reactive trajectories using a moving transition state
- Chemical reactions induced by oscillating external fields in weak thermal environments
- Transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields
- Persistence of transition state structure in chemical reactions driven by fields oscillating in time
- Reaction rate calculation with time-dependent invariant manifolds
- Improvements to Kramers Turnover Theory
- Transition State Theory for dissipative systems without a dividing surface
- A Transition State Theory for Calculating Hopping Times and Diffusion in Highly Confined Fluids