Ultrafast non-adiabatic molecular energy conversion into photons induced by quantized electromagnetic fields

Abstract

Molecular polaritons within the mid-infrared regime have emerged as a source for modifying and manipulating molecular and photonic properties. However, the development of new methodologies for photon generation is still a challenge in nanophotonics. We propose a molecular model based on the Holstein–quantum–Rabi Hamiltonian, which also incorporates realistic dipole moments and nonadiabatic couplings among electronic excited states, to study the ultrafast photodynamics of diatomic molecules in confined electromagnetic fields within quantized cavities. In addition to vibronic transitions due to intrinsic nonadiabatic couplings, two types of light-induced crossings emerge: one type is located at molecular nuclear geometries where the rotating wave approximation is fulfilled, and another type appears at different geometries where counter-rotating transitions may occur. We make a comprehensive study of polariton photodynamics within a time window of a few tens of femtoseconds, where dissipative mechanisms do not influence the polariton photodynamics. We stress the dramatic change of the polariton energy spectrum as a function of the Huang–Rhys factor when nonadiabatic couplings are included in the model. We conclude that both the molecular nonadiabatic couplings and, more specifically, the counter-rotating couplings in the cavity–molecule interaction play a crucial role in converting vibronic energy into photons through excited dressed states. We also show that the sign of the Huang–Rhys factor has a significant impact on this photon conversion. Our work paves the way for the development of many-photon generation powered by strong light–matter interaction, along with potential applications using alkaline earth monohydride molecules.