Influence of external driving on decays in the geometry of the LiCN isomerization

TL;DR

This paper applies transition state theory to study how external driving influences decay rates in the LiCN isomerization, demonstrating potential control of chemical reactions via time-dependent fields.

Contribution

It extends transition state theory to time-dependent systems and quantifies how external fields alter decay rates in LiCN isomerization.

Findings

External driving significantly affects decay rates.

External fields can control reaction dynamics.

Decay rates differ markedly from non-driven cases.

Abstract

The framework of transition state theory relies on the determination of a geometric structure identifying reactivity. It replaces the laborious exercise of following many trajectories for a long time to provide chemical reaction rates and pathways. In this paper, recent advances in constructing this geometry even in time-dependent systems are applied to the LiCN $\rightleftharpoons$ LiNC isomerization reaction, driven by an external field. We obtain decay rates of the reactant population close to the transition state by exploiting local properties of the dynamics of trajectories in and close to it. We find that the external driving has a large influence on these decay rates when compared to the non-driven isomerization reaction. This, in turn, provides renewed evidence for the possibility of controlling chemical reactions, like this one, through external time-dependent fields.