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, in a non-invasive way. A detailed theoretical description of the strong coupling regime is urgently needed to develop an intuitive picture of cavity chemistry, however, our theoretical comprehension is still in its infancy and ab initio approaches<br/>to study the mixed light-matter problem have only been developed in recent years. To ease the rationalization of cavity-induced effects on molecules, we introduce an ab initio method leading to the first fully consistent molecular orbital theory for quantum electrodynamics environments. Our non-perturbative framework explains modifications of the electronic structure due to the interaction with the photon field. 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. It also allows us to investigate electronic cavity-induced modifications of reaction mechanisms in vibrational strong coupling regimes.

Molecular orbital theory in cavity QED environments

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