Hydration free energies of monovalent ions in transferable intermolecular potential four point fluctuating charge water: An assessment of simulation methodology and force field performance and transferability

Abstract

Hydration free energies of nonpolarizable monovalent atomic ions in transferable intermolecular potential four point fluctuating charge (TIP4P-FQ) are computed using several commonly employed ion-water force fields including two complete model sets recently developed for use with the simple water model with four sites and Drude polarizability and TIP4P water models. A simulation methodology is presented which incorporates a number of finite-system free energy corrections within the context of constant pressure molecular dynamics simulations employing the Ewald method and periodic boundary conditions. The agreement of the computed free energies and solvation structures with previously reported results for these models in finite droplet systems indicates good transferability of ion force fields from these water models to TIP4Q-FQ even when ion polarizability is neglected. To assess the performance of the ion models in TIP4P-FQ, we compare with consensus values for single-ion hydration free energies arising from recently improved cluster-pair estimates and a reevaluation of commonly cited, experimentally derived single-ion hydration free energies; we couple the observed consistency of these energies with a justification of the cluster-pair approximation in assigning single-ion hydration free energies to advocate the use of these consensus energies as a benchmark set in the parametrization of future ion force fields.