Strong Coupling with Light Enhances the Photoisomerization Quantum Yield of Azobenzene

Strong coupling between molecules and light can be achieved in resonant cavities, giving rise to hybrid light-molecule states (polaritons). Chemistry in such states is different than the original photochemistry of the molecule. As such, polaritonic chemistry is emerging as a non-conventional approach to manipulate photochemical reactions, toward, for example, increasing reaction specificity or enhancing yields. Using accurate quantum chemistry multiscale simulations, we find that strong coupling can lead to enhanced photoisomerization yields for azobenzene in a realistic nanoplasmonic setup. Strong coupling acts on the motion of azobenzene atoms in the multi-dimensional space of internal coordinates, steering them away from unreactive pathways accessible instead in the traditional regimen. Our results show that the chemical complexity of molecules, rather than being a foe, can be turned into a friend in the strong coupling regimen, endowing polaritonic chemistry of additional potentialities.