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

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 interact with a resonant infrared (IR) radiation mode. An efficient theoretical approach is detailed, and numerical results are presented for the HCl, H2O, and CH4 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, absorption 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 absorption spectra, and in the intermolecular energy transfer occurring during Hermitian or non-Hermitian time propagation.