Controlling the Photostability of Pyrrole with Optical Nanocavities

[Image: see text] Strong light-matter coupling provides a new strategy to manipulate the non-adiabatic dynamics of molecules by modifying potential energy surfaces. The vacuum field of nanocavities can couple strongly with the molecular degrees of freedom and form hybrid light-matter states, termed as polaritons or dressed states. The photochemistry of molecules possessing intrinsic conical intersections can be significantly altered by introducing cavity couplings to create new conical intersections or avoided crossings. Here, we explore the effects of optical cavities on the photo-induced hydrogen elimination reaction of pyrrole. Wave packet dynamics simulations have been performed on the two-state, two-mode model of pyrrole, combined with the cavity photon mode. Our results show how the optical cavities assist in controlling the photostability of pyrrole and influence the reaction mechanism by providing alternative dissociation pathways. The cavity effects have been found to be intensely dependent on the resonance frequency. We further demonstrate the importance of the vibrational cavity couplings and dipole-self interaction terms in describing the cavity-modified non-adiabatic dynamics.