I_h对称性硼、碳原子簇化合物的从头计算（I）──B_（32）、C_2B_（30  

Ab Initio Studies on Boron and Carbon Clusters of I_h Symmetry(Ⅰ)──Geometries and Stabilities of B_(32),C_2B_(30) and B_(32)H_(32)￣(2-)

作　　者：张明瑜[1] 于微舟[1] 李晓天 

机构地区：[1]吉林大学理论化学研究所

出　　处：《高等学校化学学报》1994年第5期754-757,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：本文用从头计算方法研究了含３２个顶点的硼烷及裸原子簇Ｂ３２与Ｃ２Ｂ３０的构型、稳定性及反应活性。Ｂ３２的优化计算结果表明，１２个５配位与２０个６配位两类硼原子不在同一球面时最稳定，而且所含两种Ｂ－Ｂ核间距离（Ｒ_（５６）Ｒ_（６６））的优化值验证了Ｌｉｐｓｃｏｍｂ的经验数值。Ｂ３２、Ｂ_（３２）Ｈ_（３２）^（２－）电子结构及原子布居的计算表明骨架成键轨道满足Ｗａｄｅ规则．相应的计算还表明，中性Ｂ_（３２）Ｈ_（３２）可能稳定存在，但构型的对称性将低于Ｉｋ对称，另外．对Ｃ２Ｂ３０结合能的计算及前线轨道性质的分析表明，Ｃ２Ｂ３０热稳定性较高，并且有较强的得电子反应活性。In this paper,the ab initio calculations are carried out on the geometries,stabilities and reactivities of the boron and carbon clusters with 32 vertices. The optimization calculations show that B(32) is the most stable cluster when 12 five-coordinated and 20 six-coordinated borons are not in the same spherical surface.Two kinds of obtained B─B distances (R(56),R(66)) verify Lipscomb's a set of empirical values.The calculated results of the electron structure,total energies and the atom populations for B(32) and B(32) indicate that the number of bonding framework orbitals satisfies Wade's rule and that neutral B(32)H(32) is possibly stable,while its symmetry must be lower than Ih.For C2B(30)the calculation of the bonded energy and the analysis of the frontier orbital characters suggest that the thermal stability ofC2B(30) is higher and the reactivity of the accepted electron of it is stronger.

关 键 词：硼烷 碳硼烷 原子 簇状化合物 构型 

分 类 号：O627.31[理学—有机化学]