Role of Cavity Losses on Nonadiabatic Couplings and Dynamics in Polaritonic Chemistry

We present a non-Hermitian formulation of the polaritonic structure of azobenzene strongly coupled to a photonic mode that explicitly accounts for the fleeting nature of the photon–molecule interaction. This formalism reveals that the polaritonic nonadiabatic couplings that facilitate cis–trans isomerization can be dramatically modified by photonic dissipation. We perform Fewest-Switches Surface Hopping dynamics on the surfaces that derive from our non-Hermitian formalism and find that the polaritonic isomerization yields are strongly suppressed for moderate dissipation rates and that cavity-free isomerization dynamics are recovered under large dissipation rates. These findings highlight the important role that the finite lifetime of photonic degrees of freedom play in polaritonic chemistry.