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arXiv · 2410.11485

Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons

Tamás Szidarovszky
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Abstract

Accurate rovibrational molecular models are employed to gain insight in high-resolution into the collective effects and intermolecular processes arising when molecules in the gas phase are interacting with a resonant infrared (IR) radiation mode. An efficient theoretical approach is detailed and numerical results are presented for the HCl, H$_2$O and CH$_4$ molecules confined in an IR cavity. It is shown that by employing a rotationally resolved model for the molecules, revealing the various cavity-mediated interactions between the field-free molecular eigenstates, it is possible to obtain a detailed understanding of the physical processes governing the energy level structure, absorbtion spectra, and dynamic behavior of the confined systems. Collective effects, arising due to the cavity-mediated interaction between molecules, are identified in energy level shifts, in intensity borrowing effects in the absorbtion spectra, and in the intermolecular energy transfer occurring during Hermitian or non-Hermitian time propagation.

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Tamás Szidarovszky. 2024-10-15. Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons. https://doi.org/10.1063/5.0244977

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