Feng Dexuan, Zhang Bo, Zheng Guimei, Wan Songming, You Jinglin
Anhui Key Laboratory for Photonic Devices and Materials, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences , Hefei 230031, China.
University of Science and Technology of China , Hefei 230026, China.
Inorg Chem. 2016 Jul 18;55(14):7098-102. doi: 10.1021/acs.inorgchem.6b01020. Epub 2016 Jul 1.
Melt structures are essential to understand a variety of crystal growth phenomena of alkali-metal triborates, but have not been fully explored. In this work, Raman spectroscopy, coupled with the density functional theory (DFT) method, has been used to solve the CsB3O5 (CBO) melt structure. When the CBO crystal melts, the extra-ring B4-Ø bonds (the B-Ø bonds of BØ4 groups, Ø = bridging oxygen atom) that connect two B3O3Ø4 rings (the basic boron-oxygen unit in the CBO crystal structure) break. As a result, the three-dimensional boron-oxygen network collapses to unique polymer-like [B3O4Ø2]n chains. On the basis of the optimized [B3O4Ø2]n chain model, the CBO melt Raman spectrum was calculated by the DFT method for the first time and the calculated results confirm that the [B3O4Ø2]n chain is the primary species in the CBO melt. These results also demonstrate the capability of the combined Raman spectral and DFT method for analyzing borate melt structures.
熔体结构对于理解碱金属三硼酸盐的各种晶体生长现象至关重要，但尚未得到充分研究。在这项工作中，拉曼光谱结合密度泛函理论（DFT）方法被用于解析CsB3O5（CBO）熔体结构。当CBO晶体熔化时，连接两个B3O3Ø4环（CBO晶体结构中的基本硼氧单元）的外环B4-Ø键（BØ4基团的B-Ø键，Ø = 桥氧原子）断裂。结果，三维硼氧网络坍塌为独特的类似聚合物的[B3O4Ø2]n链。基于优化后的[B3O4Ø2]n链模型，首次通过DFT方法计算了CBO熔体拉曼光谱，计算结果证实[B3O4Ø2]n链是CBO熔体中的主要物种。这些结果还证明了拉曼光谱和DFT联合方法分析硼酸盐熔体结构的能力。
