Computational Insight into Calcium–Sulfate Ion Pair Formation

Abstract

The thermodynamics of ion pair formation between Ca2+ and SO42– has been studied using a rigid ion force field, the polarizable AMOEBA force field, and ab initio molecular dynamics simulation. The results obtained from the three methods are remarkably similar and consistent with the available experimental data and show that the ion association is driven by an increase in entropy, which can be related to the release of water molecules as previously found for Ca2+ and CO32–. Two new rigid ion force fields targeting different solvation free energies for sulfate have been developed. The comparison between static and dynamic properties of the solvated anion, as well as the pairing free energy with Ca2+, suggest that the model with the strongest solvation is more realistic, which may help to resolve the inconsistency in the current literature.