Structural and technical details of the Kirkwood-Buff integrals from the optimization of ionic force fields: focus on...

Results on the structural details of Kirkwood-Buff integrals obtained from the optimization of ionic force fields are presented. We have proposed and make use of an optimization scheme for ionic force fields, which is based on the modification of the cation-anion mixing rules, the calculation of the thermodynamics properties of various monovalent salt solutions according to the Kirkwood-Buff theory of solutions and the comparison to relevant experimental findings. Here, we complete and extend our calculations and analysis as we focus on the technical details of this optimization procedure and the case of fluorides, which have been proven difficult to handle. Important insight is given on the dependence of the radial distribution functions, the short-ranged potentials of mean force, and the Kirkwood-Buff integrals of the salt solutions on the different scaling factors in the mixing rules. Specifically, the way the structural details and inherent characteristics of the above properties are affected by the quantitative and qualitative differences in the mixing rules for a variety of common biologically relevant monovalent salts is mainly addressed. We conclude on the efficiency of this scheme, again with a focus on the fluorides. In the end, we provide a variation of the ion-pair mixing rules scaling factors with salt concentration to identify regimes for which different mixing rules prefactors lead to well-optimized force fields. All results are obtained through Molecular Dynamics simulations using previously optimized force fields for the monovalent ions.