ELEMENTS OF MARCUS THEORY OF ELECTRON TRANSFER REACTIONS

This work presents an overview of key concepts in electron transfer (ET) reactions, applying Marcus Theory to analyze reaction schemes, potential energy surfaces, and solvation effects. It investigates molecular polarization, the electronic configuration of the activated complex, and constraints on the transition state, integrating theoretical models with experimental data. The analysis emphasizes reaction barriers, rate constants, and solvent interactions, providing insights into both homogeneous and electrode-driven ET processes.

By extending Marcus Theory to electrochemical systems, this work explores ET at electrode interfaces, focusing on solvent reorganization, bond formation, and the influence of the electric double layer. It analyzes adiabatic and nonadiabatic ET mechanisms, activation overpotential, and relevant kinetic models. The text also incorporates excerpts from Nobel Laureate Rudolph A Marcus's original papers, accompanied by explanatory notes from both Marcus and the author, offering a structured interpretation of theoretical developments. It examines applications in electron and nuclear tunneling within chemical and biological systems, including bacterial photosynthesis and organic electrode reactions, thereby bridging fundamental theory with experimental observations.

Contents:

• Preface
• Introduction
• Foundations of the Theory, Its First Formulation
• Extensions, Electron Transfer at Electrodes
• Theory of Electrochemical Electron Transfer
• Inverted Free Energy Effect
• Unified General Theory of Electron Transfer Reactions
• Rate Constants, Barriers, Electron Transfer at Electrodes and in Solution: Theory versus Experiment — Electrode Reactions of Organic Compounds
• Marcus' Notes on Electron Transfer, Proton Transfer, and Electrode Kinetics
• M139 (=M146) Electron and Nuclear Tunneling in Chemical and Biological Systems

Readership: Electrochemists and Biologists.