Potentials of mean force of simple ions in ambient aqueous solution. II. Solvation structure from the three-dimensional reference interaction site model approach, and comparison with simulations

We applied the three-dimensional reference interaction site model (3D-RISM) integral equation theory with the 3D hypernetted chain (3D-HNC) closure or its partial linearization (3D-PLHNC) to obtain the potentials of mean force (PMFs) and the solvation structure of sodium chloride in ambient water. The bulk solvent correlations are treated by the dielectrically consistent site-site RISM/HNC theory (DRISM/HNC) to provide a proper description of the dielectric properties of solution and to include the case of a finite salt concentration. The PMF is calculated as a difference in the solvation free energy of an ion pair and of individual ions. We obtained and analyzed in detail the PMFs and solvation structure for ion pairs of NaCl at infinite dilution and a concentration of 1 M. The results are in reasonably good agreement with molecular dynamics simulations for the same model of the solution species. Positions and orientations of water molecules in the first solvation shell around the ion pair are deduced. The short-range hydration structure of the ion pairs at infinite dilution and at moderate concentration is very similar. Ionic ordering and clustering is found in 1 M solution. (C) 2000 American Institute of Physics. [S0021-9606(00)51021-6].