The orientation dependence of cavity-modified chemistry

TL;DR

This paper investigates how molecular orientation and geometry relaxation influence cavity-modified chemical reactions, revealing that allowing molecules to relax in the cavity can eliminate orientation dependence and alter thermodynamic predictions.

Contribution

It demonstrates that geometry relaxation significantly affects cavity-modified reaction energetics, challenging previous fixed-geometry assumptions in ab initio QED studies.

Findings

Relaxed molecules reorient to eliminate orientation dependence.

Geometry relaxation changes the predicted impact of cavities on reaction thermodynamics.

Fixed geometry calculations may lead to misleading conclusions.

Abstract

Recent theoretical studies have explored how ultra-strong light--matter coupling can be used as a handle to control chemical transformations. {\em Ab initio} cavity quantum electrodynamics (QED) calculations demonstrate that large changes to reaction energies or barrier heights can be realized by coupling electronic degrees of freedom to vacuum fluctuations associated with an optical cavity mode, provided that large enough coupling strengths can be achieved. In many cases, the cavity effects display a pronounced orientational dependence. In this Perspective, we highlight the critical role that geometry relaxation can play in such studies. As an example, we consider recent work [Nat.~Commun.~{\bf 14}, 2766 (2023)] that explored the influence of an optical cavity on Diels-Alder cycloaddition reactions and reported large changes to reaction enthalpies and barrier heights, as well as the observation that changes in orientation can inhibit the reaction or select for one reaction product or another. Those calculations used fixed molecular geometries optimized in the absence of the cavity and fixed relative orientations of the molecules and the cavity mode polarization axis. Here, we show that, when given a chance to relax in the presence of the cavity, the molecular species reorient in a way that eliminates the orientational dependence. Moreover, in this case, we find that qualitatively different conclusions regarding the impact of the cavity on the thermodynamics of the reaction can be drawn from calculations that consider relaxed versus unrelaxed molecular structures.