Molecular orbital theory in cavity QED environments

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 mole...

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Bibliographic Details
Published in:Nature communications 2022-03, Vol.13 (1), p.1368-8, Article 1368
Main Authors: Riso, Rosario R., Haugland, Tor S., Ronca, Enrico, Koch, Henrik
Format: Article
Language:English
Subjects:
639/638/563/606
639/638/563/758
639/638/563/980
Chemistry
Coupling (molecular)
Electronic structure
Humanities and Social Sciences
Methods
Molecular orbitals
multidisciplinary
Photons
Quantum electrodynamics
Reaction mechanisms
Science
Science (multidisciplinary)
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Summary: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. In this work, 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 electronic cavity-induced modifications of reaction mechanisms in vibrational strong coupling regimes. Theoretical description of light-matter coupling in the strong-coupling regime is challenging. Here the authors introduce a fully consistent ab-initio method of molecular orbital theory applicable to material systems in quantum electrodynamics environments.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-022-29003-2