The Development of a Classical Force Field To Determine the Selectivity of an Aqueous Fe(3+)-EDA Complex for TcO4(-) and SO4(2.)

Christopher D Williams; Neil A Burton; Karl P Travis; John H Harding

doi:10.1021/ct500198c

The Development of a Classical Force Field To Determine the Selectivity of an Aqueous Fe(3+)-EDA Complex for TcO4(-) and SO4(2.)

J Chem Theory Comput. 2014 Aug 12;10(8):3345-53. doi: 10.1021/ct500198c. Epub 2014 Jul 8.

Authors

Christopher D Williams^{1

2}, Neil A Burton², Karl P Travis¹, John H Harding¹

Affiliations

¹ Department of Materials Science and Engineering, University of Sheffield , Sheffield, S1 3JD, U.K.
² School of Chemistry, University of Manchester , Manchester, M13 9PL, U.K.

PMID: 26588303
DOI: 10.1021/ct500198c

Abstract

A classical force field has been developed in order to investigate the selective exchange of oxyanions (TcO4(-) vs SO4(2-)) with other ligands (H2O, Cl(-)) to an aqueous Fe(3+)-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 Fe(3+)-EDA complex in aqueous solution. In order to accurately introduce a degree of specificity for the interaction of Fe(3+) with each ligand type, force field parameters were tuned to match the results of density functional theory calculations. Preferential exchange of H2O, Cl(-), and SO4(2-) 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 (99)Tc.