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

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.

Structure and Stability of Endohedral Complexes X@(HAINH)12(X=Be,Mg,Ca,Zn,A1 ,Ga )

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.