A quantum chemistry approach to linear vibro-polaritonic IR spectra with perturbative electron-photon correlation
arxiv(2024)
摘要
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.
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