DMF-CH_nCl_(4-n)电荷转移复合物从头计算研究

Charge-transfer Complexes from DMF and CH_nCl_(4-n) withab initio Calculation

在HF/631G基组水平上对N,N二甲基甲酰胺(DMF)与氯代甲烷(CHnCl4-n,n=0～3)形成的电荷转移复合物进行从头计算研究,把复合物看作是一个超分子,探讨该系列复合物的择型性、稳定性、几何构型及电荷转移规律.结果表明,DMF与CHnCl4-n可形成一系列稳定的电荷转移复合物,其稳定性次序为DMFCHCl3>DMFCH2Cl2>DMFCH3Cl>DMFCCl4.在形成复合物的过程中包含着负电荷由电子供体DMF向电子受体CHnCl4-n的转移,其电荷转移量与稳定性次序相一致,复合物的键长也有明显的变化规律.计算结果能较好地解释实验现象.

The study on charge\|transfer complexes (considered as super moleculars) from DMF and CH\-\%n\%Cl\-\{4-\%n\}(n\%=0～3) was carried out with\% ab initio\% calculation at HF/6\|31G basis set level by taking G94W package The regularities of the structural selectivity, the stability,the charge transfer between the doner and accepter and the change of geometric parameters of the complexes were investigated The results show that some stable complexes can form from DMF and CH\-\%n\%Cl\-\{4-\%n\}(n\%=0～3) via charge\|transfer The stability of the complexes is regularly in order of DMF\|CHCl\-3>DMF\|CH\-2Cl\-2>DMF\|CH\-3Cl>DMF\|CCl\-4 The results also show that there is an obvious charge\|transfer in the process of forming the complexes, and the order of the charge\|transfer amounts from DMF to CH\-\%n\%Cl\-\{4-\%n\%\} is consistent with the order of the stability In addition, there are some obvious regularities for the change of the bonding lengths of the complexes The calculation results can satisfactorily explain some experimental regularities