The Transition State in a Noisy Environment

TL;DR

This paper introduces a method to construct a time-dependent dividing surface that eliminates recrossings in noisy environments, enabling more accurate application of Transition State Theory to reactions in fluctuating conditions.

Contribution

It presents a novel recipe for creating recrossing-free dividing surfaces in noisy environments, extending Transition State Theory's applicability.

Findings

The method effectively reduces recrossings in noisy systems.

It enables the use of Transition State Theory in fluctuating environments.

The approach improves reaction rate predictions in solution.

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.