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Charge-Transfer Chemical Reactions in Nanofluidic Fabry-P{\'e}rot Cavities

Authors :
Mauro, L
Caicedo, K
Jonusauskas, G
Avriller, Rémi
Source :
Phys. Rev. B 103, 165412 (2021)
Publication Year :
2020

Abstract

We investigate the chemical reactivity of molecular populations confined inside a nanofluidic Fabry-P{\'e}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{\'e}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.

Details

Database :
arXiv
Journal :
Phys. Rev. B 103, 165412 (2021)
Publication Type :
Report
Accession number :
edsarx.2010.05524
Document Type :
Working Paper
Full Text :
https://doi.org/10.1103/PhysRevB.103.165412