Nonadiabatic Phenomena In Molecular Vibrational Polaritons

Nonadiabatic phenomena are investigated in the rovibrational motion of molecules confined in an infrared cavity. Conical intersections (CIs) between vibrational polaritons, similar to CIs between electronic polaritonic surfaces, are found. The spectral, topological, and dynamic properties of the vibrational polaritons show clear fingerprints of nonadiabatic couplings between molecular vibration, rotation, and the cavity photonic mode. Furthermore, it is found that for the investigated system, composed of two rovibrating HCl molecules and the cavity mode, breaking the molecular permutational symmetry, by changing 35Cl to 37Cl in one of the HCl molecules, the polaritonic surfaces, nonadiabatic couplings, and related spectral, topological, and dynamic properties can deviate substantially. This implies that the natural occurrence of different molecular isotopologues needs to be considered when modeling realistic polaritonic systems.