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Current Theoretical Challenges in Proton-Coupled Electron Transfer: Electron Proton Nonadiabaticity, Proton Relays, and Ultrafast Dynamics

Journal Article · · The Journal of Physical Chemistry Letters, 2(12):1410-1416
DOI:https://doi.org/10.1021/jz200277p· OSTI ID:1082605

Proton-coupled electron transfer (PCET) reactions play an important role in a wide range of biological and chemical processes. The motions of the electrons, transferring protons, solute nuclei, and solvent nuclei occur on a wide range of time scales and are often strongly coupled. As a result, the theoretical description of these processes requires a combination of quantum and classical methods. This Perspective discusses three of the current theoretical challenges in the field of PCET. The first challenge is the calculation of electron proton nonadiabatic effects, which are significant for these reactions because the hydrogen tunneling is often faster than the electronic transition. The second challenge is the modeling of electron transfer coupled to proton transport along hydrogen-bonded networks. The third challenge is the simulation of the ultrafast dynamics of nonequilibrium photoinduced PCET reactions in solution. Insights provided by theoretical studies may assist in the design of more effective catalysts for energy conversion processes. The proton relay portion of this review is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1082605
Report Number(s):
PNNL-SA-88001; KC0307010
Journal Information:
The Journal of Physical Chemistry Letters, 2(12):1410-1416, Journal Name: The Journal of Physical Chemistry Letters, 2(12):1410-1416
Country of Publication:
United States
Language:
English

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