A theoretical investigation of gadolinium (III) solvation in molten salts

The solvation of lanthanides [here Gd(III)] in molten LiCl and KCl has been studied using a classical solvation approach, based on clusters of increasing size. In particular, density-functional calculations have been carried out on charged and neutral clusters, containing up to 35 chlorine halide molecules. A number of properties have been then evaluated and analyzed, including structural, vibrational, and thermochemical data. Special attention has also been devoted to the analysis of the local structure of the solvent surrounding the Gd3+ cation, a problem deeply investigated by experimentalists. Our results show that the charged clusters are not suitable to model the first solvation shell in such species, since their structures are strongly affected by the large electrostatic contribution. In contrast, more reliable simulations are obtained using the neutral clusters. In the latter, the coordination of Gd(III) in molten salts is computed to be 8 or 6, according to the salt LiCl or KCl. Furthermore, a good agreement is found with the experimental structural data and Raman spectra. Finally, preliminary results of potential interest for the estimation of solvation thermodynamics, a key parameter for exploiting molten salt chemistry, are reported for neutral clusters.