Abstract.
Equilibrium free-energy cycles relating oxidation and reduction potentials in solution to ionization potentials and electron affinities in the gas phase are constructed and the utilities of various levels of theory for computing particular free-energy changes within these cycles are discussed within the context of several examples. Emphasis is placed on the use of quantum-mechanical continuum solvation models to compute free energies of solvation. Key systems discussed include quinones, substituted anilines, substituted phenols, and reductive dechlorination reactions.
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Acknowledgements.
We thank Claudio Fontanesi for pointing out errors in Ref. [49]. This work was supported in part by the National Science Foundation (CHE 0203346) and the Environmental Molecular Sciences Laboratory (1813–GC5). P.W. thanks the University of Minnesota for support in the form of a Graduate Dissertation Fellowship.
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Dedicated to Prof. Jean-Louis Rivail, whose pioneering efforts in developing and exploiting continuum solvent models were critical in making quantum chemistry more applicable to solution phenomena
Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail
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Winget, P., Cramer, C. & Truhlar, D. Computation of equilibrium oxidation and reduction potentials for reversible and dissociative electron-transfer reactions in solution. Theor Chem Acc 112, 217–227 (2004). https://doi.org/10.1007/s00214-004-0577-0
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DOI: https://doi.org/10.1007/s00214-004-0577-0