高等学校化学学报

高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (5): 754.

• 论文 • 上一篇    下一篇

Ih对称性硼、碳原子簇化合物的从头计算(I)──B32、C2B30及B32H322-的构型及稳定性

张明瑜, 于微舟, 李晓天   

  1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春, 130023
  • 收稿日期:1993-07-10 修回日期:1994-03-17 出版日期:1994-05-24 发布日期:1994-05-24
  • 通讯作者: 张明瑜,女,51岁,副教授.
  • 作者简介:张明瑜,女,51岁,副教授.
  • 基金资助:

    国家自然科学基金

Ab Initio Studies on Boron and Carbon Clusters of Ih Symmetry(Ⅰ)──Geometries and Stabilities of B32,C2B30 and B32H322-

ZHANG Ming-Yu, YU Wei-Zhou, LI Xiao-Tian   

  1. Institute of Theoretical Chemistry, State Key Laboratory of Compulational Theoretical Chemistry, Jilin University, Changchun, 130023
  • Received:1993-07-10 Revised:1994-03-17 Online:1994-05-24 Published:1994-05-24

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摘要： 本文用从头计算方法研究了含32个顶点的硼烷B32H322-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(R56R66)的优化值验证了Lipscomb的经验数值。B32、B32H322-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BB32H32可能稳定存在,但构型的对称性将低于Ih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。

关键词: 硼烷, 碳硼烷, 热稳定性, 反应活性

Abstract: 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 B32 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─Bdistances (R56,R66) verify Lipscomb's a set of empirical values.The calculated results of the electron structure,total energies and the atom populations for B32 and B32H322- indicate that the number of bonding framework orbitals satisfies Wade's rule and that neutral B32H32 is possibly stable,while its symmetry must be lower than Ih.For C2B30the calculation of the bonded energy and the analysis of the frontier orbital characters suggest that the thermal stability of C2B30 is higher and the reactivity of the accepted electron of it is stronger.

Key words: Borane, Carborane, Thermal stability, Reactivity

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