Composite method for implicit representation of solvent in dimethyl sulfoxide and acetonitrile.

Abstract

A composite method for implicit representation of solvent previously developed to compute aqueous free energies of solvation is extended to accommodate the polar aprotic solvents dimethyl sulfoxide and acetonitrile. The method combines quantum mechanical calculation of the solute electronic structure with a modern dielectric continuum model for long-range electrostatic interactions with solvent and individual models for short-range interactions arising from dispersion, exchange, and hydrogen bonding. The few parameters involved are optimized to fit a standard data set of experimental solvation energies for neutrals and ions. Results are better than other models in the literature, with average errors for ions comparable to or smaller than the estimated experimental errors. Some circumstantial evidence is also obtained to support one of the competing extrathermodynamic arguments recently used to determine the solvation energies of the proton, which are needed to separate measurements of paired cation plus anion solvation energies into absolute single ion solvation energies in these solvents.