{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Fischer EW"],"funding":["Deutsche Forschungsgemeinschaft","Max-Planck-Gesellschaft"],"pagination":["2262-2269"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10910601"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["15(8)"],"pubmed_abstract":["In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency cavity modes form light-matter hybrid states, vibrational polaritons, with characteristic infrared (IR) spectroscopic signatures. Here, we introduce a molecular 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 <i>ab initio</i> quantum chemistry methods. We identify relevant electron-photon correlation effects at the 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<sub>2</sub> and Fe(CO)<sub>5</sub> vibro-polaritonic models in sound agreement with nonperturbative CBO linear response theory."],"journal":["The journal of physical chemistry letters"],"pubmed_title":["A Quantum Chemistry Approach to Linear Vibro-Polaritonic Infrared Spectra with Perturbative Electron-Photon Correlation."],"pmcid":["PMC10910601"],"funding_grant_id":["1636"],"pubmed_authors":["Fischer EW","Syska JA","Saalfrank P"],"additional_accession":[]},"is_claimable":false,"name":"A Quantum Chemistry Approach to Linear Vibro-Polaritonic Infrared Spectra with Perturbative Electron-Photon Correlation.","description":"In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency cavity modes form light-matter hybrid states, vibrational polaritons, with characteristic infrared (IR) spectroscopic signatures. Here, we introduce a molecular 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 <i>ab initio</i> quantum chemistry methods. We identify relevant electron-photon correlation effects at the 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<sub>2</sub> and Fe(CO)<sub>5</sub> vibro-polaritonic models in sound agreement with nonperturbative CBO linear response theory.","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Feb","modification":"2025-04-05T11:38:47.164Z","creation":"2025-04-05T11:38:47.164Z"},"accession":"S-EPMC10910601","cross_references":{"pubmed":["38381036"],"doi":["10.1021/acs.jpclett.4c00105"]}}