V_nB_(8(n+1))~-(n=1-3)团簇的几何结构、电子和光谱特性

基于密度泛函理论和卡里普索结构预测方法,系统研究了V_nB_(8(n+1))~-(n=1-3)团簇的几何结构、电子和光谱特性.首先,利用卡里普索结构预测方法确定了VB_(16)~-的基态结构为高对称性的C_(2v)点群对称结构.在此基态结构基础上,通过堆积的方式优化得到了V_2B_(24)~-和V_3B_(32)~-团簇的基态结构.结果显示,V_2B_(24)~-和V_3B~(32)~-团簇分别拥有高对称性的C_(4h)和D_(8d)点群对称结构.基于上述基态结构,系统分析了不同尺寸团簇的自然布局分布和自然电子组态、Mayer键级和电子局域函数.最后,讨论了不同团簇的红外、拉曼光谱等光谱特性,为过渡金属钒掺杂硼基纳米材料的研究提供理论参考.

Geometric structures, electronic and spectral properties of VnB8(n+1)- (n=1-3) clusters

In this paper, the geometric structures, electronic and spectral properties of VnB8(n+1)- (n=1-3) clusters are studied by using the density functional theory and Crystal structure Analysis by Particle Swarm Optimization (CALYPSO) searching method. First, based on the CALYPSO searching method, the lowest energy of VB16- cluster is obtained with high symmetry of C2v point group. With the assembly of VB16- clusters, two different V2B24- and V3B32- clusters are identified in the high symmetry C4h and D8d point groups, respectively. Second, the electronic properties, such as natural population analysis, natural electron configuration, Mayer bond order and electron localization functions are analyzed for the lowest energy structures of VnB8(n+1)- (n=1-3) clusters. At last, IR and Raman spectra are simulated and discussed. We hope that our researches could supply some guidelines for future theoretical and experimental studies of vanadium-doped boron based nanomaterials.