| Abstract
| - High-level density functional theory in combination with a continuum solvation model was employed tocompute standard redox potentials in solution phase for three different classes of electrochemically activemolecules: small organic molecules, metallocenes, and M(bpy)3x (M = Fe, Ru, Os; x = +3, +2, +1, 0, −1).Excellent agreement with experimentally determined redox potentials is found with an average deviation ofapproximately 150 mV when four different solvents commonly in use for electrochemical measurementswere included. To obtain quantitative agreement between theory and experiment, the use of a large basis setis crucial especially when the redox couple includes anionic species. Whereas the addition of diffuse functionsimproved the results notably, vibrational zero-point-energy corrections and addition of entropy effects areless important. The computational protocol for computing redox potentials in solution, which has beenbenchmarked, is a powerful and novel tool that will allow a molecular-level understanding of the featuresdictating the properties of redox-active species.
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