Molecular orbital theory in cavity QED environments

TL;DR

This paper introduces a novel ab initio molecular orbital theory for molecules in cavity QED environments, enabling prediction and analysis of cavity-induced modifications of molecular electronic structure and reactivity.

Contribution

It presents the first fully consistent, non-perturbative molecular orbital framework for quantum electrodynamics environments, advancing understanding of cavity effects on molecules.

Findings

Predicts cavity-induced changes in molecular reactivity

Identifies classes of systems with significant cavity effects

Analyzes vibrational strong coupling regime effects

Abstract

Coupling between molecules and vacuum photon fields inside an optical cavity has proven to be an effective way to engineer molecular properties, in particular reactivity. To ease the rationalization of cavity induced effects we introduce an ab initio method leading to the first fully consistent molecular orbital theory for quantum electrodynamics environments. Our framework is non-perturbative and explains modifications of the electronic structure due to the interaction with the photon field. We show that the newly developed orbital theory can be used to predict cavity induced modifications of molecular reactivity and pinpoint classes of systems with significant cavity effects. We also investigate cavity-induced modifications of molecular reactivity in the vibrational strong coupling regime.