Plasmonic Nanocavities Enable Self‐Induced Electrostatic Catalysis

The potential of strong interactions between light and matter remains to be further explored within a chemical context. Towards this end herein we study the electromagnetic interaction between molecules and plasmonic nanocavities. By means of electronic structure calculations, we show that self‐induced catalysis emerges without any external stimuli through the interaction of the molecular permanent and fluctuating dipole moments with the plasmonic cavity modes. We also exploit this scheme to modify the transition temperature T_1/2 of spin‐crossover complexes as an example of how strong light–matter interactions can ultimately be used to control a materials responses.