English

Linear and nonlinear vibrational excitation driven by molecular polaritons

Chemical Physics 2026-04-20 v1

Abstract

Following our recent numerical study [arXiv:2601.16299 (2026)], we investigate vibrational excitation induced by transient optical driving in molecular ensembles strongly coupled to a cavity mode using the field-driven Holstein--Tavis--Cummings model. We analyze how pulsed excitation redistributes energy among electronic, photonic, and vibrational degrees of freedom in molecular polaritons. Vibrational dynamics are examined over a broad range of pulse durations and intensities within both the single-excitation approximation and a mean-field description of collective light--matter coupling. Despite their distinct formulations and microscopic descriptions, these two approaches yield consistent scaling relations for vibrational excitation. In particular, we disentangle linear and nonlinear contributions to vibrational excitation, which are reflected in distinct quadratic and quartic scaling behaviors with respect to the driving field amplitude (that is, linear and quadratic dependence on the incident pulse intensity). The microscopic origin of the nonlinear component is identified as a polariton-mediated intrapulse stimulated Raman-like process, enabled by a pulse spectral bandwidth large enough to overlap both upper and lower polaritons (rather than a conventional multi-pulse scheme). These results establish a unified framework for understanding vibrational excitation under pulsed polariton driving and provide guidance for the interpretation and control of ultrafast polariton experiments. Discrepancies between the mean-field and single-excitation approaches under certain pulsed conditions are identified and analyzed.

Keywords

Cite

@article{arxiv.2604.15685,
  title  = {Linear and nonlinear vibrational excitation driven by molecular polaritons},
  author = {Wenxiang Ying and Carlos M. Bustamante and Franco P. Bonafé and Richard Richardson and Michael Ruggenthaler and Maxim Sukharev and Angel Rubio and Abraham Nitzan},
  journal= {arXiv preprint arXiv:2604.15685},
  year   = {2026}
}

Comments

12 pages,5 figures

R2 v1 2026-07-01T12:13:48.208Z