靛蓝及其取代物的密度泛函理论研究  

A Density Functional Theory Study of Indigo and Its Derivatives

作　　者：薛运生[1] 贡雪东[1] 肖鹤鸣[1] 田禾[2] 

机构地区：[1]南京理工大学化工学院,南京210094 [2]华东理工大学精细化工研究所,上海200237

出　　处：《化学学报》2004年第10期963-968,共6页Acta Chimica Sinica

基　　金：国家自然科学基金 (No.2 98361 50 )资助项目

摘　　要：运用量子化学中密度泛函理论 (DFT)方法 ,在B3LYP/6 3 1G 水平上对靛蓝及其芳环 4,4′ ,5 ,5′ ,6,6′ ,7,7′ 取代衍生物进行理论计算 .探讨了F ,Cl,Br,NO2 ,CH3 O ,CH3 在不同位置的取代对分子的几何构型、电子结构和电子光谱的影响 ,获得与实验结果相一致的结论 .还用含时密度泛函理论 (TD DFT)方法在相同水平计算其电子光谱 .结果表明靛蓝及其芳环取代衍生物的最低激发单重态 (S1 )均源自HOMO LUMO (π π )Indigo is one of the oldest known natural dyes. In the past decades, indigoids have been extensively investigated by experimental and theoretical methods. In theoretical study, semiempirical or Hartree-Fock MO methods were mostly used. Indigo and its 4, 4'-, 5, 5'-, 6, 6'-, and 7, 7'-disubstituted derivatives with F, Cl, Br, NO2, CH3O, and CH3 groups have been studied at the B3LYP/6-31G* level of density functional theory (DFT) in this paper. The substitution effects of the electron-donating and electron-accepting groups at various positions on the geometry structures, electronic structures, and the electronic spectra have been investigated, and quite good results were achieved compared with the experimental results. The electronic spectra have been calculated using the time-dependent density functional theory (TD-DFT) approach. The calculated results showed that the first singlet excited state of indigoids resulted from the electron transition from the highest occupied MO (HOMO) to the lowest unoccupied MO (LUMO).

关 键 词：靛蓝 密度泛函理论 量子化学 芳环 取代物 取代基效应 电子光谱 天然染料 

分 类 号：TQ610[化学工程—精细化工]