Identifying reactive trajectories using a moving transition state

TL;DR

This paper introduces a time-dependent dividing surface that efficiently identifies reactive trajectories early, reducing computational effort compared to traditional fixed transition state methods.

Contribution

The authors propose a moving transition state dividing surface that improves early identification of reactive trajectories, minimizing recrossings and computational costs.

Findings

Numerical simulations confirm the approach's efficiency.

The method reduces the need for long-time trajectory evolution.

Applicable to harmonic and moderately anharmonic systems.

Abstract

A time-dependent no-recrossing dividing surface is shown to lead to a new criterion for identifying reactive trajectories well before they are evolved to infinite time. Numerical dynamics simulations of a dissipative anharmonic two-dimensional system confirm the efficiency of this approach. The results are compared to the standard fixed transition state dividing surface that is well-known to suffer from recrossings and therefore requires trajectories to be evolved over a long time interval before they can reliably be classified as reactive or non-reactive. The moving dividing surface can be used to identify reactive trajectories in harmonic or moderately anharmonic systems with considerably lower numerical effort or even without any simulation at all.