Charge-Transfer Chemical Reactions in Nanofluidic Fabry-Pérot Cavities

We investigate the chemical reactivity of molecular populations confined inside a nanofluidic Fabry-Perot cavity. Due to strong light-matter interactions developing between a resonant electromagnetic cavity-mode and the electric dipole moment of the confined molecules, a polariton is formed. The former gets dressed by environmental vibrational and rotational degrees of freedom of the solvent. We call the resulting polariton dressed by its cloud of environmental excitation a "reacton", since it further undergoes chemical reactions. We characterize how the reacton formation modifies the kinetics of a photoisomerization chemical reaction involving an elementary charge-transfer process. We show that the reaction driving-force and reorganization energy are both modulated optically by the reactant concentration, the vacuum Rabi splitting and the de-tuning between the Fabry-Perot cavity frequency and targeted electronic transition. Finally, we compute the ultrafast picosecond dynamics of the whole photochemical reaction. We predict that despite optical cavity losses and solvent-mediated non-radiative relaxation, measurable signatures of the reacton formation can be found in state-of-the-art pump-probe experiments.