Kinetic effects of vibrational polaritons in electron transfer.*

Chemical kinetics has been modified for thermally activated reactions with molecules under vibrational strong light-matter coupling (VSC). These experiments are counterintuitive since VSC can only be achieved when a collectivity of vibrational modes (N ≈ 10¹⁰) simultaneously couples to a single confined electromagnetic mode, and, as a result, the normal modes consist of two polaritonic modes and N – 1 dark modes that behave as uncoupled vibrations. In this work, we show how VSC can induce catalysis in electron transfer, as described by the Marcus-Levich-Jortner formalism, by providing low activation energy channels that dominate the kinetics even when they are largely outnumbered by channels with unmodified activation energy.