Transferable Ion Force Fields in Water from a Simultaneous Optimization of Ion Solvation and Ion–Ion Interaction

Abstract

The poor performance of many existing nonpolarizable ion force fields is typically blamed on either the lack of explicit polarizability, the absence of charge transfer, or the use of unreduced Coulomb interactions. However, this analysis disregards the large and mostly unexplored parameter range offered by the Lennard-Jones potential. We use a global optimization procedure to develop water-model-transferable force fields for the ions K+, Na+, Cl–, and Br– in the complete parameter space of all Lennard-Jones interactions using standard mixing rules. No extra-thermodynamic assumption is necessary for the simultaneous optimization of the four ion pairs. After an optimization with respect to the experimental solvation free energy and activity, the force fields reproduce the concentration-dependent density, ionic conductivity, and dielectric constant with high accuracy. The force field is fully transferable between simple point charge/extended and transferable intermolecular potential water models. Our results show that a thermodynamically consistent force field for these ions needs only Lennard-Jones and standard Coulomb interactions.