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QED_ET__Single_ (12).pdf (3.48 MB)
Polariton Mediated Electron Transfer via Cavity Quantum Electrodynamics
Preprints are manuscripts made publicly available before they have been submitted for formal peer review and publication. They might contain new research findings or data. Preprints can be a draft or final version of an author's research but must not have been accepted for publication at the time of submission.
submitted on 13.03.2020 and posted on 16.03.2020by Arkajit Mandal, Todd D. Krauss, Pengfei Huo
We investigate the polariton mediated electron transfer
reaction in a model system. With analytic rate constant expression and direct quantum dynamical simulations, we demonstrate that charge transfer reactions can
be significantly enhanced or suppressed by coupling the
molecular system to the quantized radiation field inside
an optical cavity. This is due to the fact that quantum
light-matter interactions can mediate the effective driving force and electronic couplings between the hybrid
light-matter excitation (so-called the polariton states).
Under a resonance condition, the effective driving force
can be tuned by changing the light-matter coupling
strength; for an off-resonant condition, the same effect
can be accomplished by changing the molecule-cavity
detuning. Forming polaritons thus provides new possibilities to control the fundamental photo-redox chemistry. Further, we find that both the counter-rotating
terms and the dipole self-energy in the quantum electrodynamics Hamiltonian play a crucial role for obtaining an accurate polariton eigenenergy and the polariton mediated charge transfer rate constant, especially
in the ultra-strong coupling regime. These investigations significantly complement the previous theoretical
developments that ignore both terms, and bring interesting concepts from quantum optics into the field of