Modification of Thermal Chemical Rates in a Cavity via Resonant Effects in the Collective Regime

TL;DR

This paper explores how Fabry-Perot cavities influence thermal chemical reaction rates in gas-phase molecules, revealing mechanisms like energy dissipation and polaritonic mode interactions that accelerate reactions under collective strong coupling.

Contribution

It provides a detailed theoretical analysis of the combined effects of activated and spectator molecules on reaction rates in cavities, highlighting new mechanisms of rate modification.

Findings

Spectator molecules facilitate energy dissipation post-reaction.

Cavity-induced polaritonic modes interact with molecules at shifted resonances.

Conditions for accelerated reaction rates in the collective regime are identified.

Abstract

The modification of thermal chemical rates in Fabry-Perot cavities, as observed in experiments, still poses theoretical challenges. While we have a better grasp of how the reactivity of isolated molecules and model systems changes under strong coupling, we lack a comprehensive understanding of the combined effects and the specific roles played by activated and spectator molecules during reactive events. In this study, we investigate an ensemble of randomly oriented gas-phase HONO molecules undergoing a cis-trans isomerization reaction on an ab-initio potential energy surface. Using the classical reactive flux method, we analyze the transmission coefficient and determine conditions that lead to accelerated rates within the collective regime. We identify two main mechanisms at work: firstly, spectator molecules enhance the cavity's ability to dissipate excess energy from the activated molecule post-reactive event. Additionally, the interaction between spectator molecules and the cavity gives rise to the creation of polaritonic modes. These modes then interact with the activated molecule at a shifted resonance frequency.