THE AQUEOUS SOLVATION OF WATER - A COMPARISON OF CONTINUUM METHODS WITH MOLECULAR-DYNAMICS

The calculation of the solvation properties of a single water molecule in liquid water is carried out in two ways. In the first, the water molecule is placed in a cavity and the solvent is treated as a dielectric continuum. This model is analyzed by numerically solving the Poisson equation using the DelPhi program. The resulting solvation properties depend sensitively on the shape and size of the cavity. In the second method, the solvent and solute molecules are treated explicitly in molecular dynamics simulations using Ewald boundary conditions. We find a 2-kcal/mol difference in solvation free energies predicted by these two methods when standard cavity radii are used. In addition, dielectric continuum theory assumes that the solvent reacts solely by realigning its electric moments linearly with the strength of the solute's electric field; the results of the molecular simulation show important nonlinear effects. Nonlinear solvent effects are generally of two types: dielectric saturation, due to solvent-solute hydrogen bonds, and electrostriction, a decrease in the solute cavity due to an increased electrostatic interaction. We find very good agreement between the two methods if the radii defining the solute cavity used in the continuum theory is decreased with the solute charges, indicating that electrostriction is the primary nonlinear effect and suggesting a procedure for improvement of continuum methods. The two methods cannot be made to agree when the atomic radii are made charge independent, but charge dependent cavity radii are shown to greatly improve agreement.