A Quantum Chemistry Approach to Linear Vibro-Polaritonic Infrared Spectra with Perturbative Electron-Photon Correlation.
Eric W FischerJan A SyskaPeter SaalfrankPublished in: The journal of physical chemistry letters (2024)
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 ab initio 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 2 and Fe(CO) 5 vibro-polaritonic models in sound agreement with nonperturbative CBO linear response theory.
Keyphrases
- density functional theory
- energy transfer
- molecular dynamics
- monte carlo
- living cells
- molecular dynamics simulations
- solar cells
- climate change
- electron transfer
- electron microscopy
- molecular docking
- dna methylation
- quantum dots
- high intensity
- low birth weight
- gestational age
- metal organic framework
- room temperature