Acta Chimica Sinica ›› 2001, Vol. 59 ›› Issue (2): 207-212.

Original Articles

胺(或氨) - CHCl3系CT复合物密度泛函法研究

1. 中山大学化学与化学工程学院
• 发布日期:2001-02-15

Study on a series of CT complexes of amine(or NH3) - CHCl3 with DFT method

Zheng Kangcheng;Kuang Daibin;Mao Shucai;Shen Yong

• Published:2001-02-15

The theoretical study on a series of complexes forming from amine [ CH3NH2, (CH3)2NH and (CH3)3N] or ammonia (NH3), and CHCl3 via weak chemical interaction was carried out. The complexes were considered as supermolecules and calculated with DFT method at B3LYP/6-311G(d,p) level, and the basis set superposition error (BSSE) was corrected by the counterpoise method. The electronic structure and its related properties, e.g., regularities of the stability, the charge transfer between the donor and acceptor, and the change of geometric parameters of the complexes were investigated. The results show that the stability of the complexes is in the order: NH3－CHCl3 (Ⅰ) >CH3NH2-CHCl3(Ⅱ)>(CH3)2NH-CHCl3 (Ⅲ)>(CH3)3N-CHCl3(Ⅳ). There is an obvious charge - transfer in the process of forming the complexes. The stability of the series of complexes keeps a good linear relation to the CT amount, the energy gap △εL-H between LUMO and HOMO, and the distance of extended H - bond. In addition, it is also related to the atomic net charges of the donor center and acceptor center, etc. The analysis of the stability regularity of the complexes must be considered synthetically both of the covalent interaction and static charge interaction between the molecules. The calculation results can be better used to explain some experimental phenomean and regularities.

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