Local Coordination Environment of 3d and 4d Transition Metal Ions in LiCl-KCl Eutectic Mixture

In this study, the structure and coordination environment of two 3d transition elements (Ni and Cr) is investigated in a molten chloride salt system. Electronic absorption spectroscopy was employed to elucidate their coordination environment in 3LiCl-2KCl eutectic salt, as a function of temperature. Density functional theory (DFT) modeling was used to determine the coordination environment of the transition metal species in the eutectic composition as well as the optical spectra computationally. The Ni(2+)and Cr(3+) exist in a tetrahedral and octahedral coordination environment, respectively, in eutectic salt. The spectra thus obtained were compared with the experimental data; a reasonable qualitative agreement was obtained between experimental and computational Ni(2+) and Cr(3+)spectra, and the coordination of both elements in the eutectic composition were in excellent agreement with the experimentally determined results. Computational results were also obtained for two 4d elements, Mo(3+) and Nb(3+), with both quantum molecular dynamics (QMD) and hybrid functional optical spectra indicating octahedral coordination.