Non-Adiabatic Molecular Dynamics of Molecules in the Presence of Strong Light-Matter Interactions

The mixing between the light and matter characters modifies the photophysical and photochemical properties. In this work, a theoretical model and an efficient numerical method for studying the dynamics of molecules strongly interacting with quantum light are developed based on non-adiabatic excited-state molecular dynamics. The methodology was employed to study the cis-trans photoisomerization of a realistic molecule in a cavity. Numerical simulations demonstrate that the photochemical reactions can be controlled by tuning the properties of the cavity. In the calculated example, the isomerization is suppressed when polaritonic states develop a local minimum on the lower polaritonic state. Moreover, the observed reduction of isomerization is tunable via the photon energy and light-molecule coupling strength. But the fluctuation in transition dipole screens the effect of light-matter, which makes it harder to tune the photochemical properties via the coupling strength.