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Electrochemical Electron Transfer: Key Concepts, Theories, and Parameterization via Atomistic Simulations
Mengke Zhang1,2, Yanxia Chen1, Marko M Melander3
1Hefei National Research Center for Physical Science at Microscale and Department of Chemical Physics, University of Science and Technology of China, 230026 Hefei, China.
Chemical Reviews
|June 25, 2026
Summary
This review explains electron transfer (ET) kinetics at electrochemical interfaces, detailing theories and computational methods. It highlights how solvent dynamics and electrode interactions influence ET rates for technological applications.
Area of Science:
- Physical Chemistry
- Electrochemistry
- Computational Science
Background:
- Electron transfer (ET) at electrochemical interfaces is crucial for many technologies.
- Theoretical descriptions and computational modeling of ET kinetics are active research areas.
Purpose of the Study:
- To elucidate key concepts and theories of electron transfer kinetics.
- To focus on the coupling between solvent fluctuations and quantum electronic states.
- To explore weak, strong, and intermediate electronic coupling regimes.
Main Methods:
- Review of fundamental rate theories and reaction coordinates.
- Analysis of solvent dynamics and electrical double layer (EDL) structure.
- Highlighting atomistic simulations like density functional theory (DFT) and molecular dynamics (MD).
Main Results:
- Discussion of factors critically impacting ET kinetics, including solvent dynamics and EDL.
- Assessment of simulation tools for key assumptions and parameters (e.g., reorganization energy, electronic coupling).
Conclusions:
- Opportunities exist for advancing the field through multiscale, quantum-classical models.
- Future models should incorporate EDL effects, multiple reaction coordinates, and solvent-controlled dynamics.
- The review serves as a guide for integrating theory and simulation in electrochemical ET studies.
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