We study a simple model for photoinduced electron transfer reactions for the case of many donor–acceptor pairs that are collectively and homogeneously coupled to a photon mode of a cavity. We describe both coherent and dissipative collective effects resulting from this coupling within the framework of a quantum optics Lindblad master equation. We introduce a method to derive an effective rate equation for electron transfer by adiabatically eliminating donor and acceptor states and the cavity mode. The resulting rate equation is valid for both weak and strong coupling to the cavity mode and describes electronic transfer through both the cavity-coupled bright states and the uncoupled dark states. We derive an analytic expression for the instantaneous electron transfer rate that depends non-trivially on the time-varying number of pairs in the ground state. We find that under proper resonance conditions, and in the presence of an incoherent drive, reaction rates can be enhanced by the cavity. This enhancement persists, and can even be largest, in the weak light–matter coupling regime. We discuss how the cavity effect is relevant for realistic experiments.
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7 February 2021
Research Article|
February 02 2021
A quantum optics approach to photoinduced electron transfer in cavities
Special Collection:
Polariton Chemistry: Molecules in Cavities and Plasmonic Media
D. Wellnitz
;
D. Wellnitz
a)
1
ISIS (UMR 7006), University of Strasbourg and CNRS, and icFRC
, 67000 Strasbourg, France
2
IPCMS (UMR 7504), CNRS
, 67000 Strasbourg, France
a)Author to whom correspondence should be addressed: [email protected]
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G. Pupillo
;
G. Pupillo
b)
1
ISIS (UMR 7006), University of Strasbourg and CNRS, and icFRC
, 67000 Strasbourg, France
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J. Schachenmayer
J. Schachenmayer
c)
1
ISIS (UMR 7006), University of Strasbourg and CNRS, and icFRC
, 67000 Strasbourg, France
2
IPCMS (UMR 7504), CNRS
, 67000 Strasbourg, France
Search for other works by this author on:
D. Wellnitz
1,2,a)
G. Pupillo
1,b)
J. Schachenmayer
1,2,c)
1
ISIS (UMR 7006), University of Strasbourg and CNRS, and icFRC
, 67000 Strasbourg, France
2
IPCMS (UMR 7504), CNRS
, 67000 Strasbourg, France
a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on Polariton Chemistry: Molecules in Cavities and Plasmonic Media.
J. Chem. Phys. 154, 054104 (2021)
Article history
Received:
November 13 2020
Accepted:
January 10 2021
Citation
D. Wellnitz, G. Pupillo, J. Schachenmayer; A quantum optics approach to photoinduced electron transfer in cavities. J. Chem. Phys. 7 February 2021; 154 (5): 054104. https://doi.org/10.1063/5.0037412
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