A quantum chemistry approach to linear vibro-polaritonic IR spectra with perturbative electron-photon correlation
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arXiv
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| Formato: | Preprint |
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2024
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| _version_ | 1866912738455846912 |
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| author | Fischer, Eric W. Syska, Jan A. Saalfrank, Peter |
| author_facet | Fischer, Eric W. Syska, Jan A. Saalfrank, Peter |
| contents | 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. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2401_02188 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | A quantum chemistry approach to linear vibro-polaritonic IR spectra with perturbative electron-photon correlation Fischer, Eric W. Syska, Jan A. Saalfrank, Peter Chemical Physics 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. |
| title | A quantum chemistry approach to linear vibro-polaritonic IR spectra with perturbative electron-photon correlation |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2401.02188 |