NANS7016 NANO1: Theory and Simulation of Electrochemical Electron Transfer Kinetics (JSS35) (2 op)

Electron transfer (ET) at electrochemical interfaces lies at the heart of numerous energy conversion and storage processes, including fuel cells, batteries, and CO₂ reduction technologies. Despite its conceptual foundations being established decades ago, the theoretical treatment of ET remains a complex and evolving subject, particularly due to the intricate coupling between classical solvent fluctuations and quantum electronic states of metal electrodes and redox species, as well as the inherent complexity of solvent dynamics and electric double layer (EDL) effects. A comprehensive understanding of how these factors collectively influence ET kinetics is fundamental to optimizing electrochemical energy conversion and storage devices.

In recent years, advances in atomistic simulation techniques—such as density functional theory (DFT) and molecular dynamics (MD) simulations—have enabled increasingly detailed and accurate microscopic descriptions of electrochemical ET. These methods have provided critical mechanistic insights into interfacial charge transfer processes. However, due to their high computational cost, they are typically limited to small, idealized systems and relatively short timescales, which restricts their direct applicability to experimental or technologically relevant conditions.

A promising strategy to overcome these limitations is to combine physically motivated conceptual models with parameters extracted from atomistic simulations, thereby integrating microscopic accuracy with theoretical scalability; establishing this connection is the central aim of this course, which will:

1) Provide a unified conceptual and theoretical framework for electrochemical ET

(2) Parameterize conceptual theory with atomistic simulations.

(3) Integrate ET and EDL theories to achieve a more comprehensive and realistic modeling of electrochemical ET kinetics.

(4) Assess the limitations and advances the theoretical and computational modeling of electrochemical ET.

The course is largely based on a review article the lecturers have submitted to Chemical Reviews (arxiv preprint: https://doi.org/10.48550/arXiv.2510.24635). The course covers topics such as:

· General chemical rate theory and transition state theory

· Rate theory for electron transfer (ET) reactions

· Marcus theory for molecular and electrochemical ET kinetics

· Atomistic simulation of ET rates

· Effective, physical models of ET kinetics

· Solvent dynamics and non-adiabatic effects

· Influence of the reaction environment on ET rates: Frumkin corrections and beyond

· Hierarchical modeling of electrocatalytic reactions

· Open questions and future directions in ET theory and simulation      

· Understand the connections between general rate theory and electron transfer kinetics

· Learn the central factors controlling electron transfer kinetics and how they are described theory theoretical methods

· Learn the key equations and their merits/limitations for describing electron transfer kinetics

· Design and analyze atomistic simulations to parametrize the key equations