The Development of a Classical Force Field To Determine the Selectivity of an Aqueous Fe3+–EDA Complex for TcO4– and SO42–

A classical force field has been developed in order to investigate the selective exchange of oxyanions (TcO4? vs SO42?) with other ligands (H2O, Cl?) to an aqueous Fe3+?ethylenediamine (EDA) complex. Potentials of mean force for a range of exchange reactions were generated using umbrella sampling and classical molecular dynamics simulations in order to calculate the affinity of each oxyanion for the Fe3+?EDA complex in aqueous solution. In order to accurately introduce a degree of specificity for the interaction of Fe3+ with each ligand type, force field parameters were tuned to match the results of density functional theory calculations. Preferential exchange of H2O, Cl?, and SO42? for TcO4? via an interchange mechanism is observed, in agreement with experimental observations. Both the relative solvation entropies and enthalpies of the anions were found to be critically important factors governing the magnitude of the observed selectivities. These results have important implications for the design and modeling of functionalized materials for the remediation of land contaminated with radioactive 99Tc.