Na+–Na+ and Cl−–Cl− ion pairs in water: Mean force potentials by constrained molecular dynamics

Abstract

Molecular dynamics simulations of Na++Na+, Na++Cl−, and Cl−+Cl− ions in dilute aqueous solution were carried out using a flexible single point charge (SPC) model for water. The resulting structural and dynamic properties are compared with experimental data and other computer simulation results. The potentials of mean force [W(r)] between the like ions were determined from constrained molecular dynamics simulations. The resulting W(r) for the Na+–Na+ ion pair is in qualitative agreement with other computer simulation findings, whereas the discrepancies are important in the case of the Cl−–Cl− ion pair. Our Cl−–Cl− mean force potential shows a moderate minimum which does not involve the unexpected strong attraction between chloride ions at short distances as predicted in earlier papers. The solvent structure around the ion pairs for separations corresponding to the maxima and minima of the W(r)’s is analyzed.