Dipole Effects on Electron Transfer are Enormous |
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| Authors: | Dr Maciej Krzeszewski Eli M Espinoza Dr Ctirad Červinka James B Derr John A Clark Dr Dan Borchardt Prof Gregory J O Beran Prof Daniel T Gryko Prof Valentine I Vullev |
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| Institution: | 1. Department of Bioengineering, University of California, Riverside, Riverside, CA, USA;2. Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland;3. Present address: Graduate School of Science, Nagoya University, Nagoya, Japan;4. Department of Chemistry, University of California, Riverside, Riverside, CA, USA;5. Department of Physical Chemistry, University of Chemistry and Technology, Prague 6—Dejvice, Czech Republic;6. Department of Biochemistry, University of California, Riverside, Riverside, CA, USA |
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| Abstract: | Molecular dipoles present important, but underutilized, methods for guiding electron transfer (ET) processes. While dipoles generate fields of Gigavolts per meter in their vicinity, reported differences between rates of ET along versus against dipoles are often small or undetectable. Herein we show unprecedentedly large dipole effects on ET. Depending on their orientation, dipoles either ensure picosecond ET, or turn ET completely off. Furthermore, favorable dipole orientation makes ET possible even in lipophilic medium, which appears counterintuitive for non‐charged donor–acceptor systems. Our analysis reveals that dipoles can substantially alter the ET driving force for low solvent polarity, which accounts for these unique trends. This discovery opens doors for guiding forward ET processes while suppressing undesired backward electron transduction, which is one of the holy grails of photophysics and energy science. |
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| Keywords: | charge transfer dipoles electron transfer kinetics Rehm-Weller equation |
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