Fuller Jon, Phillips William, An Qi, Gakhar Ruchi
Idaho National Laboratory, Pyrochemistry and Molten Salt Systems Department, Idaho Falls, ID 83415, USA.
Department of Chemical and Materials Engineering, University of Nevada, Reno, NV 89577, USA.
Materials (Basel). 2022 Feb 16;15(4):1478. doi: 10.3390/ma15041478.
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 Niand Cr 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 and Crspectra, 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 and Nb, with both quantum molecular dynamics (QMD) and hybrid functional optical spectra indicating octahedral coordination.
在本研究中，研究了两种3d过渡元素（Ni和Cr）在熔融氯化物盐体系中的结构和配位环境。采用电子吸收光谱法来阐明它们在3LiCl-2KCl共晶盐中作为温度函数的配位环境。密度泛函理论（DFT）建模用于确定共晶组成中过渡金属物种的配位环境以及计算光谱。在共晶盐中，Ni和Cr分别存在于四面体和八面体配位环境中。将由此获得的光谱与实验数据进行比较；实验和计算得到的Ni和Cr光谱之间获得了合理的定性一致性，并且两种元素在共晶组成中的配位与实验测定结果非常吻合。还对两种4d元素Mo和Nb进行了计算，量子分子动力学（QMD）和混合泛函光谱均表明其为八面体配位。
