靛族染料发色体电子光谱性质的含时密度泛函理论研究  

TDDFT study on electronic spectrum property for indigoid chromophores

作　　者：薛运生[1] 贡雪东[2] 肖鹤鸣[2] 田禾[3] 印晓星[1] 

机构地区：[1]徐州医学院药学系,江苏徐州221002 [2]南京理工大学化工学院,江苏南京210094 [3]华东理工大学精细化工研究所,上海200237

出　　处：《分子科学学报》2005年第1期6-11,共6页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(29836150)

摘　　要：　采用密度泛函方法(DFT)在B3LYP/631+G 水平上对一系列靛族染料发色体的几何构型进行优化计算;在获得基态稳定结构的基础上,应用含时密度泛函理论(TDDFT)在相同水平下计算其电子吸收光谱.探讨了不同给电子基团和发色体的延伸对电子吸收光谱的影响,得到了与对应母体化合物一致的变化规律.结果表明,给电子基团给电子能力的增强和发色体的纵向延伸分别使光谱产生一定红移和轻微的蓝移.通过对前线轨道组成进行自然布居分析,揭示了靛族染料的发光均源自分子中HOMOLUMO(π→π*)电子跃迁.The geometrical structures of indigoid chromophores have been studied at the B3LYP/6-31+G^(*) level of density functional theory(DFT).Subsequently,the electronic absorption spectrum has been calculated by using the time-dependent density functional theory (TD-DFT) approach at the same level.The effects of the electron-donating groups and the extension of chromophores on the electronic spectrum have been investigated,and good results are achieved compared with the experimental results of indigoids.The result indicates that absorption band of chromophore suffers bathochromic shift when electron-donating capability is increased and minor hypsochromic shift when the chromophore is extended.In addition,the frontier molecular orbital composition was analysed by natural population analysis (NPA),which indicates that the emission of indigoids originate from the electronic HOMOLUMO(π→π^(*)) transitions.

关 键 词：靛族染料 发色体 含时密度泛函理论 电子吸收光谱 分子结构 还原染料 

分 类 号：TQ613.3[化学工程—精细化工]