Accelerated Hydrogen Exchange Reaction in a Dark Cavity: A Benchmark for Bridging the Gap Between Theory and Experiment (2507.09695v1)

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.