Vibro-polaritonic Raman spectroscopy via cavity Born-Oppenheimer perturbation theory
Abstract
We derive a vibro-polaritonic Raman activity from third-order cavity Born-Oppenheimer perturbation theory (CBO-PT) accounting for weak interactions between electrons and low-frequency cavity modes in the vibrational strong coupling (VSC) regime. This work extends the recently presented CBO-PT linear response approach [J. Phys. Chem. Lett. 2024, 15, 2262-2269] from infrared (IR) to vibro-polaritonic Raman spectroscopy. In a first step, we discuss cavity-induced corrections to the static dipole polarizability tensor, which manifest as molecular and cavity mode contribution determined by the polarization-projected static hyperpolarizability tensor. We then obtain the corresponding vibro-polaritonic Raman activity in double harmonic approximation, which contains molecular, cavity and mixed contributions similar to previously discussed CBO-PT IR intensities. The cavity Raman activity can be interpreted as effective transmission component, which is exclusively determined by the polaritonic Raman response. The methodology and its relation to vibro-polaritonic IR spectroscopy is illustrated for a formaldehyde molecule under VSC. An implementation of the CBO-PT linear response approach for vibro-polaritonic Raman and IR spectroscopies is provided via the open-source Python package CBOvibSpec.
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BibTeX
@misc{fischer2026vibropolaritonic,
title = {{Vibro-polaritonic Raman spectroscopy via cavity Born-Oppenheimer perturbation theory}},
author = {Eric W. Fischer},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.23483},
eprint = {2610.23483},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.23483},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Vibro-polaritonic Raman spectroscopy via cavity Born-Oppenheimer perturbation theory
AU - Eric W. Fischer
PY - 2026
DA - 2026/10/16
PB - arXiv
DO - 10.48550/arxiv.2610.23483
UR - https://arxiv.org/abs/2610.23483
AB - We derive a vibro-polaritonic Raman activity from third-order cavity Born-Oppenheimer perturbation theory (CBO-PT) accounting for weak interactions between electrons and low-frequency cavity modes in the vibrational strong coupling (VSC) regime. This work extends the recently presented CBO-PT linear response approach [J. Phys. Chem. Lett. 2024, 15, 2262-2269] from infrared (IR) to vibro-polaritonic Raman spectroscopy. In a first step, we discuss cavity-induced corrections to the static dipole polarizability tensor, which manifest as molecular and cavity mode contribution determined by the polarization-projected static hyperpolarizability tensor. We then obtain the corresponding vibro-polaritonic Raman activity in double harmonic approximation, which contains molecular, cavity and mixed contributions similar to previously discussed CBO-PT IR intensities. The cavity Raman activity can be interpreted as effective transmission component, which is exclusively determined by the polaritonic Raman response. The methodology and its relation to vibro-polaritonic IR spectroscopy is illustrated for a formaldehyde molecule under VSC. An implementation of the CBO-PT linear response approach for vibro-polaritonic Raman and IR spectroscopies is provided via the open-source Python package CBOvibSpec.
ER -