Simple Two-Body Cation−Water Interaction Potentials Derived from ab Initio Calculations. Comparison to Results Obtained with an Empirical Approach

Ab initio calculations were performed on M(H2O)n systems, M being Li+, Na+, K+, Be2+, Mg2+, or Ca2+, with n = 1, 2, 4, or 6. For the most hydrated systems, parameters for the effective Lennard-Jones interaction between the cation and the water molecules were determined, so as to reproduce ab initio results. In order to compare our results to those obtained previously by J. Aqvist with a purely empirical approach, water−water interactions were assumed to be given by the TIP3P model. Different forms for the effective two-body interaction potential were tested. The best fits of ab initio data were obtained with a smooth r-7 repulsive and a classical r-4 attractive term, in addition to standard Coulombic interactions. Though better fits were obtained for alkaline cations than for alkaline-earth ones, only Be2+ obviously requires a more complicated form of the potential energy function.The corresponding parameters were tested with molecular dynamics simulations of cations in water solutions and with hydration ...