Charge-Transfer Chemical Reactions in Nanofluidic Fabry-P{é}rot Cavities

Abstract

We investigate the chemical reactivity of molecular populations confined inside a nanofluidic Fabry-P{é}rot 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-P{é}rot 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.

References in corpus (5)

• Input-output theory of cavities in the ultra-strong coupling regime: the case of a time-independent vacuum Rabi frequency
• Quantum theory of collective strong coupling of molecular vibrations with a microcavity mode
• Electron transfer in confined electromagnetic fields
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• Vacuum-Induced Symmetry Breaking of Chiral Enantiomer Formation in Chemical Reactions
• Dissociation slowdown by collective optical response under strong coupling conditions
• Understanding polaritonic chemistry from ab initio quantum electrodynamics
• Angular Momentum-Dependent Spectral Shift in Chiral Vacuum Cavities
• Electron transfer in confined electromagnetic fields: a unified Fermi's golden rule rate theory and extension to lossy cavities
• Not dark yet: strong light-matter coupling can accelerate singlet fission dynamics