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采用杂化密度泛函理论B3LYP方法在6-31G(d.p)水平对三(2-吡啶基甲基)胺(TPMA)及其卤素阴离子复合物进行结构优化。在复合物的形成过程中,通过计算几何结构参数、电荷布居、前线轨道和热力学参数,深入研究了主体分子和卤素阴离子(F和C1~-)之间的超分子作用。研究结果表明,TPMA识别卤素阴离子是一个自发反应。在复合物的形成过程中,主体分子的前线轨道与客体阴离子发生了相互作用。电子从卤素阴离子的HOMO轨道转移到主体分子的LUMO轨道。并且,形成的TPMA-F~-复合物比TPMA-C~-更为稳定,这一计算结果与文献报道的TPMA阴离子识别实验结果相一致。
The structural optimization of tris (2-pyridylmethyl) amine (TPMA) and its halogen anion complex at the level of 6-31G (d.p) was carried out by the hybrid density functional theory B3LYP method. During the formation of the complex, the supramolecular interactions between the host molecule and halogen anions (F and C1 ~ -) were studied in depth by calculating geometrical parameters, charge population, frontier orbital and thermodynamic parameters. The results show that TPMA recognition of halogen anions is a spontaneous reaction. During the formation of the complex, the frontier orbit of the host molecule interacts with guest anions. Electrons migrate from the HOMO orbitals of the halogen anions to the LUMO orbitals of the host molecule. Moreover, the formation of TPMA-F ~ - complex is more stable than that of TPMA-C ~. This calculation is in good agreement with the TPMA anion recognition reported in the literature.