Stochastic Transition States: Reaction Geometry amidst Noise

Abstract

Classical transition state theory (TST) is the cornerstone of reaction rate theory. It postulates a partition of phase space into reactant and product regions, which are separated by a dividing surface that reactive trajectories must cross. In order not to overestimate the reaction rate, the dynamics must be free of recrossings of the dividing surface. This no-recrossing rule is difficult (and sometimes impossible) to enforce, however, when a chemical reaction takes place in a fluctuating environment such as a liquid. High-accuracy approximations to the rate are well known when the solvent forces are treated using stochastic representations, though again, exact no-recrossing surfaces have not been available. To generalize the exact limit of TST to reactive systems driven by noise, we introduce a time-dependent dividing surface that is stochastically moving in phase space such that it is crossed once and only once by each transition path.

References in corpus (1)

• The Transition State in a Noisy Environment

Cited by in corpus (19)

• Identifying reactive trajectories using a moving transition state
• Obtaining time-dependent multi-dimensional dividing surfaces using Lagrangian descriptors
• Chemical dynamics between wells across a time-dependent barrier: Self-similarity in the Lagrangian descriptor and reactive basins
• 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
• Invariant Manifolds and Rate Constants in Driven Chemical Reactions
• Scaling perspective on Intramolecular vibrational energy flow: analogies, insights, and challenges
• Persistence of transition state structure in chemical reactions driven by fields oscillating in time
• Binary contraction method for the construction of time-dependent dividing surfaces in driven chemical reactions
• Reaction rate calculation with time-dependent invariant manifolds
• Transition State Theory for dissipative systems without a dividing surface
• Neural network approach to time-dependent dividing surfaces in classical reaction dynamics
• Influence of external driving on decays in the geometry of the LiCN isomerization
• Phase-space geometry of the generalized Langevin equation
• Transition State Theory for solvated reactions beyond recrossing-free dividing surfaces
• Neural network approach for the dynamics on the normally hyperbolic invariant manifold of periodically driven systems
• Controlling reaction dynamics in chemical model systems through external driving
• Dynamics and bifurcations on the normally hyperbolic invariant manifold of a periodically driven system with rank-1 saddle
• Thermal decay rates of an activated complex in a driven model chemical reaction