New Implicit Solvation Models for Dispersion and Exchange Energies

Abstract

Implicit solvation models provide a very efficient means to estimate solvation energies. For example, dielectric continuum models are commonly used to obtain the long-range electrostatic interactions. These may be parametrized to also include in some average manner short-range interactions such as dispersion and exchange, but it is preferable to instead develop additional implicit models specifically designed for the short-range interactions. This work proposes new models for dispersion and exchange interactions between solute and solvent by adapting approaches previously developed for treatment of gas-phase intermolecular forces. The new models are formulated in terms of the charge densities of the solutes and use only three adjustable parameters. To illustrate the performance of the models, electronic structure calculations are reported for a large number of solutes in two nonpolar solvents where short-range interactions dominate and different balances pertain between attractive dispersion and repulsive exchange contributions. After empirical optimization of the requisite parameters, it is found that the errors compared to experimental solvation free energies are only about 0.4 kcal/mol on average, which is better than previous approaches in the literature that invoke many more parameters.