Calculation of solvation free energies with DCOSMO-RS.

Abstract

The concept of dielectric continuum models has turned out to be very fruitful for the qualitative description of solvation effects in quantum chemical calculations, although from a theoretical perspective its basis is questionable, at least if applied to polar solvents, because the electrostatic nearest neighbor interactions in polar solvents are much too strong to be described by macroscopic dielectric continuum theory. On the basis of this insight, the Conductorlike Screening Model for Realistic Solvation (COSMO-RS) had been developed, which gives a thermodynamically consistent, quantitative description of solvation effects in polar and nonpolar solvents, even in mixtures and at variable temperature, starting from quantum chemical calculations of solute and solvent molecules embedded in a virtual conductor (COSMO). Though COSMO-RS usually only requires quantum chemical calculations in the conductor and thus does not allow for studying of the concrete solvent influence on the solute electron density, the direct COSMO-RS (DCOSMO-RS) has been introduced, which uses the σ-potential, i.e., a solvent specific response function provided by COSMO-RS, as a replacement of the conductor or dielectric response employed in continuum solvation models. In this article we describe the current status of DCOSMO-RS and demonstrate the performance of the DCOSMO-RS approach for the prediction of free energies of solvation.