Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons (2410.11485v3)

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.