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Resonant vibrational strong coupling (VSC) between molecular vibrations and quantized field modes of low-frequency optical cavities constitutes the conceptual cornerstone of vibro-polaritonic chemistry. In this work, we theoretically investigate complementary nonresonant interactions between electrons and low-frequency cavity modes with a focus on cavity-induced modifications of electronic interactions in molecular ensembles under VSC. Methodologically, we combine cavity Born-Oppenheimer perturbation theory (CBO-PT) Fischer, Saalfrank, JCTC 19, 7215 (2023) with ab initio wave function approaches, specifically, CBO Hartree-Fock and coupled cluster theories. In a first step, we derive cavity-induced energy corrections to intra- and intermolecular electronic energies based on second-order CBO-PT. We find local modifications of molecular PES for selected isomerization reactions to be small and dominantly captured by the first-order dipole-fluctuation correction. Excellent agreement between CBO-PT and non-perturbative methods is obtained, which indicates potentially negligible state relaxation effects under VSC. Secondly, we examine cavity-modified intermolecular interactions revealing non-trivial corrections of dipole-dipole, dipole-induced dipole and van-der-Waals type character emerging at second-order of CBO-PT. Besides an explicit coupling of interacting dimers to cavity modes, we find a cavity-polarization dependent enhanced long-range component of dipole-induced dipole and van-der-Waals interactions. We present an illustrative numerical analysis of interaction potentials for selected molecular dimer models based on the CBO-CCSD approach, which provides a non-perturbative perspective on cavity-modified intermolecular interactions under VSC.
Eric W. Fischer (Wed,) studied this question.