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Density functional reactivity theory characterizes charge separation propensity in proton-coupled electron transfer
Shubin Liu1, Daniel H Ess, Cynthia K Schauer
1Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, United States. shubin@email.unc.edu
The Journal of Physical Chemistry. A
|April 22, 2011
Summary
Proton-coupled electron transfer (PCET) reactions involve electron transfer distant from proton sites. Density functional reactivity theory reveals the electron transfer site is not the proton acceptor site in these crucial energy processes.
Area of Science:
- Physical Chemistry
- Quantum Chemistry
- Chemical Physics
Background:
- Proton-coupled electron transfer (PCET) reactions are fundamental to biological and artificial solar energy conversion.
- Understanding electron and proton movement is key to optimizing energy transfer efficiency.
Purpose of the Study:
- To characterize electron transfer propensity in PCET reactions using advanced theoretical methods.
- To identify the specific sites of electron transfer relative to proton acceptor sites.
Main Methods:
- Employing density functional reactivity theory (DFRT).
- Utilizing the dual descriptor and electrophilic Fukui function.
- Analyzing hydrogen bond and van der Waals reactant complexes.
Main Results:
- DFRT descriptors successfully characterized electron transfer propensity.
- The electrophilic regions of reactant complexes were identified.
- Analysis confirmed electron transfer occurs away from the proton acceptor site.
Conclusions:
- The electrophilic region, indicating electron transfer, does not encompass the proton acceptor site in PCET reactions.
- This finding provides critical insights for designing efficient artificial photosynthesis and energy conversion systems.
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