Computational electrochemistry: prediction of liquid-phase reduction potentials

Abstract

This article reviews recent developments and applications in the area of computational electrochemistry. Our focus is on predicting the reduction potentials of electron transfer and other electrochemical 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) with 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), and the Marcus theory of electronic charge transfer. We also review 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.

Structural, topological and vibrational properties of an isothiazole derivatives series with antiviral activities

“…1. The optimization of each structure in aqueous solution was performed at the same level of theory by using the SCRF method and the PCM model [21,22] while the solvation energies were computed with the solvation model [23]. The Moldraw program was used to calculate the volume variations of all the derivatives in aqueous solution [24] The natural population atomic (NPA) charges, bond orders and stabilization energies were calculated by using the NBO [25,26] calculations while the atomic Merz-Kollman (MK) charges were used to compute the molecular electrostatic potentials [29].…”

Ab Initio Electrochemistry: Exploring the Hydrogen Evolution Reaction on Carbon Nanotubes

“…An extensive comparison of the various literature values is presented in ref. 28. According to Isse and Gennaro,27 this discrepancy is related to choice of energy zero level and the actual definition of the absolute potential.…”

Free Energies of Redox Half-Reactions from First-Principles Calculations

“…EC-F D originates from the integrated heat capacity and the entropic contribution for an electron assuming the electron convention and Fermi-Dirac statistics[1,51,52] (-0.038 eV). ∆E(SHE → N HE) corresponds…”