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

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

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Gaussian03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.

Based on our previous research work of closo-hedral cluster （HAINH）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 sixmembered 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.