Potentials of mean force of simple ions in ambient aqueous solution. I. Three-dimensional reference interaction site model approach

We adapt the three-dimensional reference interaction site model (3D-RISM) to calculate the potentials of mean force for ion–molecular solution as a difference between the chemical potential of solvation of a cluster of solutes and of individual ones. The method yields the solvation structure around the cluster of solutes in detail. The solvation chemical potential is obtained for the three-dimensional hypernetted chain (3D-HNC) closure as well as for its partial linearization (3D-PLHNC approximation). The solvation chemical potential is obtained in a closed analytical form for both the 3D-HNC and 3D-PLHNC closures. The 3D-RISM integral equations are solved by using the supercell technique. A straightforward supercell treatment of ionic solute in polar molecular solvent leads to a big error in the potential of mean force as well as the solvation chemical potential, which for simple ions in water amounts to about 35 kcal/mol. We elaborated corrections to the 3D-RISM integral equations, alleviating the artif...

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