Transition path sampling and the calculation of rate constants

TLDR

The method departs from earlier dynamical approaches by not requiring prior knowledge or explicit transition state definitions. It uses importance sampling to statistically characterize transition states, demonstrated on a simple model. We developed a method that transforms reactive flux correlation calculations into reversible work computations, enabling rate constant determination for rare‑event transitions in complex systems.

Abstract

We have developed a method to study transition pathways for rare events in complex systems. The method can be used to determine rate constants for transitions between stable states by turning the calculation of reactive flux correlation functions into the computation of an isomorphic reversible work. In contrast to previous dynamical approaches, the method relies neither on prior knowledge nor on explicit specification of transition states. Rather, it provides an importance sampling from which transition states can be characterized statistically. A simple model is analyzed to illustrate the methodology.