三硝基苯-对位取代苯酚负离子荷移复合物从头算研究

Study on Charge Transfer Complexes of Trinitrobenzene with Substituted Phenolate Anions by Ab Initio Calculation

运用G94W量子化学程序,在HF/3-21G基组水平上对三硝基苯-对位取代苯酚(取代基:CH_3O-,CH_3-,Cl-)负离子的电荷转移复合物进行从头计算。把电荷转移复合物看成一个超分子,研究该系列复合物的稳定性、电荷转移及几何构型等规律。计算结果表明,苯酚负离子供电中心O沿一倾角指向三硝基苯中的任意相邻两个硝基之间的C位置上,复合物的稳定性按对位取代苯酚取代基CH_3O-,CH_3-,Cl-的次序减小,与实验规律相一致。计算结果还表明,形成该系列复合物具有明显的电荷转移,其稳定性与电荷转移量有关等。

The study on charge transfer complexes of 1,3,5 - trinitrobenzene with substituted phenolate anions (substituents CH3O - , CH3 - , Cl - ) was carried out using ab initio calculation at HF/ 3 - 21G basis set level (G94W package) . The entire charge transfer complex was taken as a hyper -molecule in the calculation. The regularities of the stability, the charge transfer and the geometrie configuration of the complexes were investigated .The cumulation results show that the donor center 0 atom in subsituted phenolate anions points to C atom between any two nitro groups in trinitrobenzene along a dip angle during forming the complexes. The stabilities of the complexes regularly decrease according to the order of substituents CH3O - , CH3 - , Cl in substitued phenolate anions, it agrees with the experimental results satisfactorily. The calculation results also show that there is an obvious charge transfering in the process of forming the series of complexes, and the stabilities of the complexes are related to the quantities of the charge transfering.