三硼酸铋晶体及其高温熔体结构的拉曼光谱研究  

Microstructure Study on Bismuth Triborate Crystal and Its Melt at High Tempera ture by Raman Spectroscopy

作　　者：季自方[1] 尤静林[1,2,3] 西蒙.派特里克 王媛媛[1] 侯敏[1] 王丽红[1] 张国春[4] 万松明[5] 傅佩珍[4] 吴以成[4] 殷绍唐[5] 

机构地区：[1]上海大学材料科学与工程学院,上海200072 [2]法国国家科学研究中心高温和辐射研究所 [3]奥尔良大学,法国奥尔良4507145067 [4]中国科学院理化技术研究所,北京100190 [5]中国科学院安徽光学精密机械研究所,安徽合肥230031

出　　处：《光谱学与光谱分析》2012年第1期127-131,共5页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(50932005;20973107;40973046);法国LE STUDIUM项目资助

摘　　要：测量了BiB3O6晶体从常温到熔融态的拉曼光谱,考察了其温致结构变化和预测了熔体的结构基元。同时,采用量子化学从头计算和密度泛函理论对拉曼光谱进行了计算和结构分析。结果表明,随着温度的升高,对包含阳离子Bi的外部晶格和[BO3]3-硼氧三角形基团结构的温致结构影响有限,却有效地削弱了[BO4]5-硼氧四面体基团结构,其松弛度增加,稳定性变差,并在熔体结构中彻底消失。研究表明BiB3O6熔体主要以硼氧六元环[B6O12]6-的形式存在,阳离子Bi起电荷平衡作用,其氧配位数为3,有别于晶体中的6。Temperature dependent Raman spectra of BiB3O 6 crystal and its melt were recorded and the microstructure of BiB3O6 melt w as predicted.Multiple theoretical methods including quantum chemistry ab init io calculation and DFT（Density Function Theory） methods were applied to simul ate the BiB3O6 crystal and melt structure and Raman spectra.It was demonstr ated that B—O triangles and Bi lattice in the crystal reveal little affected in structure while B—O tetrahedra shows severe distortion with increasing tempera ture,especially B—O tetrahedra disappears after being completely melt.The mic rostructure of BiB3O6 melt consists of six-member ring, 6-,which varies in bond lengths and angles individually.Cation Bi behaves to balance the charge of anion cluster,and the oxygen coordination number of ca tion Bi is 3,different from the crystal situation in which cation Bi is coordin ated with 6 oxygens.

关 键 词：三硼酸铋 高温拉曼光谱 熔体结构 量子化学计算 硼氧六元环 

分 类 号：O657.3[理学—分析化学]