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Published on: September 18, 2019
Correlated Reaction Coordinate Motion Produces Nonadditive Rate Enhancement for Electron and Energy Transfer in
Hanggai Nuomin1, Feng-Feng Song2, Peng Zhang1
1Department of Chemistry, Duke University, Durham, North Carolina 27708, United States.
Abstract:
Molecular structures with multiple donor, bridge, or acceptor units can display quantum interference effects that influence electron and energy transfer (ET and EnT) rates. Recent experiments found a 4-5-fold increase in ET rates for donor-acceptor structures with two acceptors compared to one. This result is surprising: simple classical or quantum analysis suggests a factor of 2 rate enhancement. We analyze the coupling interactions in multi-acceptor systems and find that rate enhancements beyond additive effects arise from acceptor-acceptor interactions that (1) shift the reaction free energy, (2) change the donor-acceptor couplings, and (3) alter the reaction-coordinate motion. Consideration of these effects explains the observed rates in multiacceptor systems and suggests strategies to tailor energy and electron transfer kinetics.
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