ABSTRACT
I. Introduction .......................................................................................................................... 229 II.Formal Dešnitions, Electrochemical Concepts, and Basic Considerations ......................... 231
A.Ionization Potentials and Electron Afšnities ................................................................231 B.Standard versus Formal Potentials ...............................................................................232 C.Cyclic Voltammetry ......................................................................................................233 D. Effects of Protonation ...................................................................................................234 E.Reversible and Irreversible Redox Processes ................................................................235 F.Liquid Junction Potentials .............................................................................................235 G.Reference Electrodes .................................................................................................... 236
III.Computation of Reduction Potentials ................................................................................... 236 A. Gas-Phase Free Energies of Reaction ........................................................................... 237
1.Gibbs Free Energy and the Treatment of Nuclear Motion .....................................237 2.Electronic Energies of Atoms and Molecules ........................................................240 3.Standard State of the Electron ............................................................................... 241
B.Free Energies of Solvation ............................................................................................ 242 1. Absolute Potential of the Aqueous SHE ................................................................243 2.Nonaqueous Systems .............................................................................................244
