Optical Cavity Manipulation and Nonlinear UV Molecular Spectroscopy of Conical Intersections in Pyrazine.

Optical cavities provide a versatile platform for manipulating the excited-state dynamics of molecules via strong light-matter coupling. We employ optical absorption and two-multidimensional electronic spectroscopy simulations to investigate the effect of optical cavity coupling in the nonadiabatic dynamics of photoexcited pyrazine. We observe the emergence of a novel polaritonic conical intersection (PCI) between the electronic dark state and photonic surfaces as the cavity frequency is tuned. The PCI could significantly change the nonadiabatic dynamics of pyrazine by doubling the decay rate constant of the S