Vacuum field in a cavity, light-mediated vibrational coupling, and chemical reactivity

Abstract

Collective coupling between vibrations of molecules, participating in reaction, and the vacuum field of a microfluidic optical cavity is now sometimes considered to be one of the novel potential unconventional ways of influencing the reaction rate. Herein, this effect is theoretically analyzed focusing on adiabatic reactions occurring via the ground electronic state with a saddle point located between reactants and products. The key conclusion is that for cavities with a relatively large number of reactants (~106-107) the scales of the corresponding corrections of the pre-exponential factor and activation energy are nearly negligible.