Do Molecular Geometries Change Under Vibrational Strong Coupling?

TL;DR

This paper investigates how molecular geometries of H$_2$O and H$_2$O$_2$ change under vibrational strong coupling with optical cavities, using ab-initio methods to understand the structural effects of light-matter interactions.

Contribution

It introduces an ab-initio approach to study molecular geometry changes under strong vibrational coupling, considering multiple cavity modes and deriving a simple estimation model.

Findings

Cavity modes influence molecular reorientation and relaxation.

Including multiple cavity modes alters the geometric effects.

A simple model based on polarizability and dipole moments estimates cavity effects.

Abstract

As pioneering experiments have shown, strong vibrational coupling between molecular vibrations and light modes in an optical cavity can significantly alter molecular properties and even affect chemical reactivity. However, the current theoretical description is limited and far from complete. To explore the origin of this exciting observation, we investigate how the molecular structure changes under strong light-matter coupling using an ab-initio method based on the cavity Born-Oppenheimer Hartree-Fock ansatz. By optimizing H$_2$O and H$_2$O$_2$ resonantly coupled to cavity modes, we study the importance of reorientation and geometric relaxation. In addition, we show that the inclusion of one or two cavity modes can change the observed results. On the basis of our findings, we derive a simple concept to estimate the effect of the cavity interaction on the molecular geometry using the molecular polarizability and the dipole moments.