本文采用量子化学从头计算方法对FLiNaK-ZrF4体系中锆的不同配位结构及不同阳离子的影响进行了模拟计算, 锆的配位数与其特征峰的峰位呈线性关系。对不同配比的FLiNaK-ZrF4体系样品进行拉曼光谱实验, 结果表明, 随着ZrF4含量的增加, 体系中自由F-浓度减小, 导致锆的配位数降低并出现桥氟结构。高温熔融状态下, FLiNaK-0.37ZrF4样品中六配位结构分解形成五配位和七配位结构。

Ab initio calculation was used to simulate Raman spectra of FLiNaK-ZrF4 system with different zirconium coordination number and the effect of different cations, the position of characteristic peaks were in linear relationship with the coordination numbers of zirconium.FLiNaK-ZrF4system with different ratios of zirconium tetrafluoride were recorded by Raman spectrometer, it indicated that the concentration of free fluoride ion decreased with the increase content of zirconium tetrafluoride, it led to the coordination number of zirconium decreasing and the appearance of briding fluorides.The configuration of six-coordination zirconium transformed into five-coordination and seven-coordination zirconium in the molten salt of FLiNaK-0.37ZrF4.