Hydration of Heavy Alkaline-Earth Cations Studied by Molecular Dynamics Simulations and X-ray Absorption Spectroscopy

The physicochemical properties of the three heaviest alkaline-earth cations, Sr2+, Ba2+, and Ra2+ in water have been studied by means of classical molecular dynamics (MD) simulations. A specific set of cation- water intermolecular potentials based on ab initio potential energy surfaces has been built on the basis of the hydrated ion concept. The polarizable and flexible model of water MCDHO2 was adopted. The theoretical-experimental comparison of structural, dynamical, energetic, and spectroscopical properties of Sr2+ and Ba2+ aqueous solutions is satisfactory, which supports the methodology developed. This good behavior allows a reasonable reliability for the predicted Ra2+ physicochemical data not experimentally determined yet. Simulated extended X-ray absorption fine-structure (EXAFS) and X-ray absorption near-edge spectroscopy spectra have been computed from the snapshots of the MD simulations and compared with the experimental information available for Sr2+ and Ba2+. For the Ra2+ case, the Ra L-3-edge EXAFS spectrum is proposed. Structural and dynamical properties of the aqua ions for the three cations have been obtained and analyzed. Along the [M(H2O)(n)](m+) series, the M-O distance for the first-hydration shell is 2.57, 2.81, and 2.93 A for Sr2+, Ba2+, and Ra2+, respectively. The hydration number also increases when one is going down along the group: 8.1, 9.4, and 9.8 for Sr2+, Ba2+, and Ra2+, respectively. Whereas [Sr(H2O)(8)](2+) is a typical aqua ion with a well-defined structure, the Ba2+ and Ra2+ hydration provides a picture exhibiting an average between the ennea- and the deca-hydration. These results show a similar chemical behavior of Ba2+ and Ra2+ aqueous solutions and support experimental studies on the removal of Ra-226 of aquifers by different techniques, where Ra2+ is replaced by Ba2+. A comparison of the heavy alkaline ions, Rb+ and Cs+, with the heavy alkaline-earth ions is made.

Automated summary

The physicochemical properties of Sr2+, Ba2+, and Ra2+ in water were studied using classical molecular dynamics simulations, showing satisfactory theoretical-experimental comparisons. Analysis of the hydration shell structures and dynamics revealed differences in hydration numbers and M-O distances among the three ions. The similarity between Ba2+ and Ra2+ aqueous solutions was highlighted, supporting experimental studies on Ra-226 removal by replacing Ra2+ with Ba2+.