物理化学学报 >> 2006, Vol. 22 >> Issue (06): 684-690.doi: 10.1016/S1872-1508(06)60027-2

研究论文 上一篇    下一篇

羰基硼化合物(BCO)n(n==1～12)的理论研究

张晓清;贾建峰;武海顺;裴晓琴   

  1. 山西师范大学化学与材料科学学院, 山西 临汾 041004
  • 收稿日期:2005-11-21 修回日期:2006-02-08 发布日期:2006-05-31
  • 通讯作者: 武海顺 E-mail:wuhs@mail.sxtu.edu.cn

Theory Investigation of (BCO)n(n=1～12)

ZHANG Xiao-Qing;JIA Jian-Feng;WU Hai-Shun;PEI Xiao-Qin   

  1. School of Chemistry and Material Science, Shanxi Normal University, Linfen 041004, P. R. China
  • Received:2005-11-21 Revised:2006-02-08 Published:2006-05-31
  • Contact: WU Hai-Shun E-mail:wuhs@mail.sxtu.edu.cn

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摘要： 运用HF/3-21G方法和密度泛函理论(DFT)的B3LYP/6-31G*方法, 对羰基硼化合物(BCO)n(n=1~12)的各种可能结构进行了优化, 对在B3LYP/6-31G*水平上得到的几何构型、电子态、结合能、振动频率、核独立化学位移(NICS)、能量二次差分和热力学性质进行了理论研究, 得到了(BCO)n(n=1~12)结构的稳定性信息. 十二种基态结构都是端配位(μ1-CO), (BCO)n(n=1~3, 5, 6) 的基态是线型或平面结构, (BCO)n(n=4, 7~12)的基态是笼状结构; B—C平均键能呈现奇偶交替现象, 偶数的结构比奇数稳定; 能量二次差分得到同样的结论；羰基的振动频率与实验值非常吻合; 热力学性质的研究对实验具有重要的指导意义.

关键词: 密度泛函理论, 结构与稳定性, 核独立化学位移, 结合能, 能量二次差分

Abstract: The structures of the (BCO)n(n=1~12) compounds were studied by HF(Hartree-Fock)/3-21G and B3LYP of density functional theory (DFT) with a basis set of 6-31G*. By discussing the geometries, electron structures, vibrational frequencies, B—C average bonding energies, nucleus independent chemical shifts (NICS), and energy secondary differences of the most stable structures at the B3LYP/6-31G* level, the stability information of the (BCO)n(n=1~12) compounds was obtained. The carbonyls of ground state of the (BCO)n(n=1~12) are μ1-CO. The most stable structures are linear or planar for the compounds (BCO)n(n=1~3, 5, 6), and polyhedron cages for (BCO)n(n=4, 7~12). Analyses of the B—C average binding energies and energy secondary differences of the most stable structures at the B3LYP/6-31G* level provides theoretic interpretation for experiment results.

Key words: Density functional theory, Structure and stability, Nucleus-independent chemical shift, Binding energy, Energy secondary differences