Computational Electrochemistry: Prediction of Liquid-Phase Reduction Potentials

Marenich, A. V.; Ho, J.; Coote, M. L.; Cramer, C. J.; Truhlar, D. G.
Phys. Chem. Chem. Phys. 2014, 16, 15068 (doi:10.1039/c4cp01572j).

This article reviews recent developments and applications in the area of computational electrochemistry. Our focus is on predicting the reduction potentials of electron transfer reactions and half-reactions in both aqueous and nonaqueous solutions. Topics covered include various computational protocols that combine quantum mechanical electronic structure methods (such as density functional theory) and implicit-solvent models, explicit-solvent protocols that employ Monte Carlo or molecular dynamics simulations (for example, Car-Parrinello molecular dynamics using the grand canonical ensemble formalism), the Marcus theory of electron charge transfer, and computational approaches based on empirical relationships between molecular and electronic structure and electron transfer reactivity. The scope of the implicit-solvent protocols is emphasized, and the present status of the theory and future directions are outlined.