草酰胺衍生物桥联双核镍配合物从头算研究

Ab Initio Study on Oxamide Derivative Bridged Binuclear Nickel(II) Complex

采用LanL2DZ基组 ,对N,N′ 双(2 苯甲酸根)草酰胺桥联双核镍配合物Ni(obbz)Ni(H2O)4 进行从头计算研究 ,探讨该配合物单、三重态的电子组态的稳定性、电子结构特征及电子自旋布居规律等。计算结果表明 ,该配合物分子的三重态比单重态稳定 ,因此 ,该配合物择型于三重态的电子组态。电子自旋主要布居于八面体环境的Ni(1)中心上 ,而处于四方配位环境的Ni(2)中心则没有发现电子自旋布居。同时 ,Ni(2)中心主要参与的分子轨道都处于低能区 ,表明Ni(2)中心的配位是相当稳定的 ,这与实验规律相符。

The investigation of the oxamide derivative bridged binuclear nickel(II) complex Ni(obbz)Ni(H2O)4 has been carried out with ab initio calculation and LanL2DZ basis set . The stabilities in singlet and triplet configuations of the complex, the characteristics of its electronic structure and the regularities of spin populations of electrons were discussed. It is indicated from the calculations that the triplet electronic configuration of the complex is more stable than the singlet one, and then the complex prefers to take the triplet configuration,e.g., the paramagnetic configuration. The spin populations of electrons are predominantly located on the Ni(1) center in octahedron coordination and no any population is found on the Ni(2) center in tetragonal coordination. In addition, the molecular orbitals participated from the atomic orbitals of Ni(2) with a rather amount locate on the lower energy area, and then the coordination structure of Ni(2) centre is rather stable. It is agreeing with experimental regularities satisfactorily.