Experimental and molecular dynamics studies of dysprosium(III) salt solutions for a better representation of the microscopic features used within the binding mean spherical approximation theory

Alexandre Ruas; Philippe Guilbaud; Christophe Den Auwer; Christophe Moulin; Jean-Pierre Simonin; Pierre Turq; Philippe Moisy

doi:10.1021/jp0609636

Experimental and molecular dynamics studies of dysprosium(III) salt solutions for a better representation of the microscopic features used within the binding mean spherical approximation theory

J Phys Chem A. 2006 Oct 19;110(41):11770-9. doi: 10.1021/jp0609636.

Authors

Alexandre Ruas¹, Philippe Guilbaud, Christophe Den Auwer, Christophe Moulin, Jean-Pierre Simonin, Pierre Turq, Philippe Moisy

Affiliation

¹ DEN/DRCP/SCPS, CEA-Valrhô Marcoule, BP 17171, 30207 Bagnols-sur-Cèze Cedex, France.

PMID: 17034172
DOI: 10.1021/jp0609636

Abstract

This work is aimed at a predictive description of the thermodynamic properties of actinide(III) salt solutions at high concentration and 25 degrees C. A new solution of the binding mean spherical approximation (BIMSA) theory, based on the Wertheim formalism, for taking into account 1:1 and also 1:2 complex formation, is used to reproduce, from a simple procedure, experimental osmotic coefficient variation with concentration for three binary salt solutions of the same lanthanide(III) cation: dysprosium(III) perchlorate, nitrate, and chloride. The relevance of the fitted parameters is discussed, and their values are compared with available literature values. UV-vis/near-IR, time-resolved laser-induced fluorescence spectroscopy experiments, and molecular dynamics (MD) calculations were conducted for dilute to concentrated solutions (ca. 3 mol.kg-1) for a study of the microscopic behavior of DyCl3 binary solutions. Coupling MD calculations and extended X-ray absorption fine structure led to the determination of reliable distances. The MD results were used for a discussion of the parameters used in the BIMSA.