Modeling Free Energies of Solvation and Transfer

Giesen, D. J.; Chambers, C. C.; Hawkins, G. D.; Cramer, C. J.; Truhlar, D. G.
in Computational Thermochemistry: Prediction and Estimation of Molecular Thermodynamics, ACS Symposium Series, Volume 677, Irikura, K., Frurip, D. J., Eds.; American Chemical Society: Washington DC, 1998; 285.

The free energy of transfer of a solute from one medium to another, which is the free energy of solvation if the first medium is the gas phase and the second is a liquid-phase solution, controls all solvation and partitioning phenomena. The SM5.4 quantum mechanical solvation model allows for the calculation of (i) partitioning free energies between the gas phase and a solvent (i.e., free energies of solvation) or (ii) partitioning free energies between two solvents. The model provides a framework for interpreting the factors responsible for differential solvation effects and can be used to predict solvation effects on chemical equilibria and kinetics--examples in this chapter include partitioning of the nucleic acid bases between water and chloroform, solvation effects on anomeric conformational equilibria, and solvation effects on the rate of the Claisen rearrangement.

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