本文利用原位高温拉曼光谱技术并结合量子化学从头计算方法研究了Li2O-WO3二元系钨酸盐熔体中稳定存在的结构单元随成分变化的趋势,给出了其在不同成分下微结构的具体模型,并对其主要振动模式进行了归属。研究表明成分不同会导致四面体基团聚合形成不同长度的链状,且Li2O与WO3摩尔比越小,也即WO3的含量越多,其链的长度越长；结合量子化学从头计算理论分析,认为当熔体的摩尔比为1∶1、1∶2、1∶3以及1∶4时,对应的阴离子基团模型分别为[WO4]2-、[W2O7]2-、[W3O10]2-和[W4O13]2-,其中[W2O7]2-、[W3O10]2-和[W4O13]2-分别由两个、三个、四个[WO4]2-以共顶形式连接而成。

Joint analysis of in-situ high-temperature Raman spectroscopy and quantum chemical ab initio calculation on the evolution of the structure units existed stably in melts with the compositions within Li2O-WO3binary system was carried out and the specfic model clusters of the micro structures in melts with different compositions were proposed in this paper,and the major vibrational modes were also assigned successfully.Results indicate that different compositions of melt result in the formation of chains of various lengths from joined [WO4]2-tetrahedra vertices,and smaller mole ratio of Li2O/WO3tends to form longer chains.The following conclusion can be made based on the simulated results of quantum chemistry ab initio calculation:when the mole ratio of Li2O/WO3in the melt is 1∶1,1∶2,1∶3 and 1∶4,the corresponding anion complex is [WO4]2-,[W2O7]2-,[W3O10]2-and [W4O13]2-,respectively.And the [W2O7]2-,[W3O10]2-and [W4O13]2- are made up of two,three and four [WO4]2-by sharing their corner oxygen atoms,respectively.