A quantum chemistry approach to linear vibro-polaritonic IR spectra with perturbative electron-photon correlation (2401.02188v1)

Abstract: In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency cavity modes form light-matter hybrid states, named vibrational polaritons, with characteristic IR spectroscopic signatures. Here, we introduce a quantum chemistry based computational scheme for linear IR spectra of vibrational polaritons in polyatomic molecules, which perturbatively accounts for nonresonant electron-photon interactions under VSC. Specifically, we formulate a cavity Born- Oppenheimer perturbation theory (CBO-PT) linear response approach, which provides an approximate but systematic description of such electron-photon correlation effects in VSC scenarios, while relying on molecular ab initio quantum chemistry methods. We identify relevant electron-photon correlation effects at second-order of CBO-PT, which manifest as static polarizability-dependent Hessian corrections and an emerging polarizability-dependent cavity intensity component providing access to transmission spectra commonly measured in vibro-polaritonic chemistry. Illustratively, we address electron-photon correlation effects perturbatively in IR spectra of CO$_2$ and Fe(CO)$_5$ vibropolaritonic models qualitatively in sound agreement with non-perturbative CBO linear response theory.