Molecular orbital theory in cavity QED environments

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.

arXiv comment23 pages, 7 figures

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• Cavity Born-Oppenheimer Coupled Cluster Theory: Towards Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime
• Deep quantum Monte Carlo approach for polaritonic chemistry
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• Scalable Quantum Monte Carlo Method for Polariton Chemistry via Mixed Block Sparsity and Tensor Hypercontraction Method