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Related Experiment Videos

Proton-coupled electron transfer

R I Cukier1, D G Nocera

  • 1Department of Chemistry, Michigan State University, East Lansing 48824-1322, USA. cukier@argus.cem.msu.edu

Annual Review of Physical Chemistry
|February 6, 1999
PubMed
Summary

Proton-coupled electron transfer (PCET) is a key charge transfer mechanism. This review clarifies consecutive (ET/PT) versus concerted (ETPT) pathways and evaluates PCET theory using model systems.

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Area of Science:

  • Physical Chemistry
  • Biophysical Chemistry
  • Materials Science

Background:

  • Proton-coupled electron transfer (PCET) is a fundamental charge transfer process.
  • PCET is crucial in biological systems (e.g., photosynthesis) and materials science (e.g., catalysis).

Purpose of the Study:

  • To review and clarify the mechanisms of PCET.
  • To distinguish between consecutive (electron transfer/proton transfer, ET/PT) and concerted (electron transfer proton transfer, ETPT) pathways.
  • To discuss model systems for testing PCET theory and evaluate rate constants.

Main Methods:

  • Formulation of the distinction between ET/PT and ETPT reaction channels.
  • Presentation of rate-constant expressions for both channels.
  • Application of dielectric continuum theory for rate constant evaluation.
  • Analysis of electron donor-hydrogen-bonded-interface-electron acceptor systems.

Main Results:

  • Theoretical framework distinguishing ET/PT and ETPT mechanisms is provided.
  • Rate-constant expressions for both PCET pathways are derived.
  • Model reaction complexes demonstrate PCET reactivity, with evaluated rate constants for ETPT and ET/PT channels.

Conclusions:

  • PCET is a versatile mechanism with distinct sequential and concerted pathways.
  • Model systems and theoretical approaches, including dielectric continuum theory, are essential for understanding PCET kinetics.
  • The study provides a foundation for experimental testing and theoretical development of PCET processes.

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