Accelerated Hydrogen Exchange Reaction in a Dark Cavity: A Benchmark for Bridging the Gap Between Theory and Experiment

TL;DR

This study demonstrates how strong light-matter coupling inside a resonant cavity can significantly modify hydrogen exchange reaction rates, providing a new platform to bridge the gap between theoretical predictions and experimental observations in polariton chemistry.

Contribution

The paper introduces cavity-induced control of hydrogen exchange reactions, highlighting isotope effects and reaction modifications within a resonant cavity, advancing polariton chemistry understanding.

Findings

Cavity coupling alters reaction rates despite small isotope effects.

New reaction pathways involve photon emission inside the cavity.

Hydrogen exchange reactions can be controlled via strong light-matter interactions.

Abstract

The gas-phase hydrogen exchange reaction (HER) is the most fundamental chemical process for benchmarking quantum reaction dynamics. In this Letter, we focus on controlling HER by means of strong light-matter coupling inside a resonant cavity, an approach often called polariton chemistry. In particular, we focus on the isotopic variation of HER involving collisions between molecular hydrogen H$_2$ and deuterium atom D, i.e., H$_2$+D$\to$HD+H. We find that the asymmetry introduced by the different isotopes, despite being small, enables strong cavity-induced modifications of reaction rates. Outside of the cavity the reaction is as usual D+H${_2}$$\to$DH+H. However, inside the cavity another type of reactions take place where D+H$_2$$\to$DH+H+E$_{photon}$, where E$_{photon}$=$\hbar\omega_{cav}$. Our results show that HER is an ideal platform to make a significant step toward closing the gap between theory and experiment in polariton chemistry.