Wan Songming, Zhang Bo, Yao Yanan, Zheng Guimei, Zhang Shujie, You Jinglin
Anhui Key Laboratory for Photonic Devices and Materials, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences , Hefei 230031, China.
School of Material Science and Engineering, Shanghai University , Shanghai 200072, China.
Inorg Chem. 2017 Nov 20;56(22):14129-14134. doi: 10.1021/acs.inorgchem.7b02263. Epub 2017 Oct 31.
The LiMoO melt structure and its Raman spectral characteristics are the key for establishing the composition-structure relationship of lithium molybdate melts. In this work, Raman spectroscopy, factor group analysis, and density functional theory (DFT) were applied to investigate the structural and spectral details of the H-LiMoO crystal and a LiMoO melt. Factor group analysis shows that the crystal has 171 vibrational modes (84A + 87A), including three acoustic modes (3A), six librational modes (2A + 4A), 21 translational modes (7A + 14A), and 141 internal modes (75A + 66A). All of the A modes are Raman-active and were assigned by the DFT method. The LiMoO melt structure was deduced from the H-LiMoO crystal structure and demonstrated by the DFT method. The results show that the LiMoO melt is made up of Li ions and MoO groups, each of which is formed by four corner-sharing MoOØ/MoOØ tetrahedra (Ø = bridging oxygen). The melt has three acoustic modes (3A) and 54 optical modes (54A). All of the optical modes are Raman-active and were accurately assigned by the DFT method.
LiMoO熔体结构及其拉曼光谱特征是建立钼酸锂熔体组成-结构关系的关键。在本工作中，采用拉曼光谱、因子群分析和密度泛函理论（DFT）研究了H-LiMoO晶体和LiMoO熔体的结构及光谱细节。因子群分析表明，该晶体有171种振动模式（84A + 87A），包括三种声学模式（3A）、六种平动模式（2A + 4A）、21种平移模式（7A + 14A）和141种内禀模式（75A + 66A）。所有A模式都是拉曼活性的，并通过DFT方法进行了归属。LiMoO熔体结构由H-LiMoO晶体结构推导得出，并通过DFT方法得到证实。结果表明，LiMoO熔体由锂离子和MoO基团组成，每个MoO基团由四个共角的MoOØ/MoOØ四面体（Ø = 桥氧）形成。熔体有三种声学模式（3A）和54种光学模式（54A）。所有光学模式都是拉曼活性的，并通过DFT方法进行了准确归属。
