物理化学学报 >> 2008, Vol. 24 >> Issue (03): 405-410.doi: 10.3866/PKU.WHXB20080309

研究论文 上一篇    下一篇

内含式复合物X@(HAlNH)12 (X=Be,Mg, Ca, Zn, Al+, Ga+)的结构和稳定性

张彩云; 崔丽亚; 武海顺   

  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:2007-10-12 修回日期:2007-11-06 发布日期:2008-03-10
  • 通讯作者: 武海顺 E-mail:wuhs@mail.sxnu.edu.cn

Structure and Stability of Endohedral Complexes X@(HAlNH)12 (X=Be,Mg, Ca, Zn, Al+, Ga+)

ZHANG Cai-Yun; CUI Li-Ya; WU Hai-Shun   

  1. Institute of Chemistry and Material Science, Shanxi Normal University, Linfen 041004, Shanxi Province, P. R. China
  • Received:2007-10-12 Revised:2007-11-06 Published:2008-03-10
  • Contact: WU Hai-Shun E-mail:wuhs@mail.sxnu.edu.cn

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摘要： 在研究闭式多面体(HAlNH)12簇合物几何构型及稳定性的基础上, 用DFT的B3LYP方法在6-31G(d)的水平上, 对其内含式复合物X@(HAlNH)12 (X= Be, Mg, Ca, Zn, Al+, Ga+)进行了构型优化和能量计算, 并讨论了稳定结构的几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系. 用Gaussian 03的QST3方法确定了客体X通过笼面6-元环的迁移过渡态(TS)结构, 并用IRC方法对所得TS结构进行了验证. 最后得到内含式复合物X@(HAlNH)12结构在热力学和动力学上的稳定性信息, 其中复合物Ga+@(HAlNH)12的结构相对最稳定.

关键词: 结构和稳定性, 包含能, 变构能, 核独立化学位移, 迁移过渡态

Abstract: Based on our previous researchwork of closo-hedral cluster (HAlNH)12, the geometries, natural bond orbital, vibrational frequency, energetic parameters, magnetic shielding constants, and nucleus independent chemical shifts of stable endohedral X@(HAlNH)12 complexes (X=Be, Mg, Ca, Zn, Al+, Ga+) were studied at the B3LYP/6-31G(d) level of density functional theory. The transition states (TS) of guest X shifting from the cage center toward a face of six-membered ring were investigated by the QST3 method of Gaussian 03 package and demonstrated with intrinsic reaction coordinate (IRC). It was found that the X@(HAlNH)12 complexes (X=Be,Mg, Zn, Al+, Ga+) were kinetically stable structures, and the complex Ga+@(HAlNH)12 was energetically favorable than the other complexes in thermodynamics.

Key words: Structure and stability, Inclusion energy, Deformation energy, Nucleus independent chemical shifts, Exit transition state

MSC2000: 

  • O641