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

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.

Raman spectroscopic study of trivalent lanthanides in concentrated aqueous solutions

“…Our data correspond with the results, obtained in [14] for aqueous solutions of the dysprosium (III) chloride using the UV-vis/near-IR, time-resolved laser-induced fluorescence spectroscopy experiments and molecular-dynamic calculations conducted for dilute to concentrated solutions (ca. 3.1 mol kg -1 ).…”

“…3.1 mol kg -1 ). The authors concluded that the 1 st coordination sphere of Dy 3+ aq was filled with 8 water molecules, while there were 17‚18 molecules in the 2 nd sphere; when the solution concentration was increased to 3.1 mol kg -1 the average number in the second sphere decreased from 17.5 to 10 and the average number of Cl -ions increased from 0.5 to 6.3; up to concentrations C~3 M the chloride ion did not form the inner-sphere complexes with dysprosium (III) [14].…”

Solute‐Induced Microstructural Transition from Weak Aggregates towards a Curved Film of Surface‐Active Extractants

“…[44] Eu 3 + LJ parameters were determined to reproduce its experimental structural properties in solution, using the Eu 3 + atomic polarizability calculated by ClavaguØra et al [45] The NO 3 À anion was described by the polarizable model defined in a previous study. [34,[46][47][48] These sets of parameters have already provided results in good agreement with experimental data. [46] Atomic partial charges on DMDOHEMA were calculated with the restricted electrostatic potential (RESP) procedure [49] (partial charges on the amide oxygen, ether oxygen and nitrogen atoms of the diamide are respectively : q OA = À0.577, q OE = À0.402 and q N = À0.613).…”

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd3+: Complex Formation, Structure, and Transmetallation

“…is plotted in Figure 4 over a large temperature range around 298 K. According to Table 1, r 1 is dominated by the IS contribution r IS 1 given in Equation (22). The temperature dependence of r IS 1 stems from that of the factors…”

“…[15] A general challenge is the accurate description of the thermodynamics, structure, and kinetics of interaction of solvent and solute molecules with Ln 3 + ions in aqueous and organic solutions. The problem arises not only for the optimization of Gd 3 + based contrast agents, [16][17][18][19][20] but also for the interactions of the radioactive trivalent actinide ions Am 3 + and Cm 3 + with humic substances modelled by those of Ln 3 + with simple species [21] and for the difficult liquid-liquid separation of these actinide ions from the Ln 3 + ions [22,23] during the reprocessing of the used nuclear fuel. In-depth theoretical efforts have been devoted to the production of accurate force fields between Ln 3 + and the surrounding molecules.…”