摘要
采用量子化学中密度泛函理论(DFT)的B3LYP方法分别用6-31G*和6-311+G*基组对苯胺、对氯苯胺和对甲苯胺及其氰乙基衍生物的几何构型进行全优化,探讨了氨基上氰乙基的引入对分子电荷转移、前线轨道能量和电子光谱等性质的影响规律.在此基础上采用含时密度泛函方法(TD-DFT)计算了分子第一激发态的电子跃迁能,得到最大吸收波长λmax.计算结果表明,氨基上氰乙基的引入,对前线分子轨道组成影响虽然小,但使得最大吸收波长红移,与实验值λmax有较好的一致性,发现该类物质主要吸收光谱源于分子内的π→π*的电子跃迁.
The impact of introducing cyanoethy groups in aromatic amines on structure,charge transfer,frontier orbital energy and composition,as well as electronic absorption spectra was investigated in this work. Theoretical studies of aniline,p-chloroaniline,p-toluidine,and cyanoethy derivatives were carried out at density functional theory （DFT） B3LYP/6-31G＊ and B3LYP/6-311＋G＊ levels to obtain optimized geometrical structures. Time-dependent density functional theory was applied to calculate the first excited state electronic transition energy and maximum absorption wavelength λmax. Our results indicate that the introduction of a cyanoethy group has limited effect on the composition of frontier orbitals. The main absorption spectrum originates from the featured π →π＊ electronic transition. The predicted spectra agree well with the available experimental findings.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2009年第4期701-706,共6页
Acta Physico-Chimica Sinica
基金
2009年度湖南省研究生创新基金
2008年度中南林业科技大学研究生创新基金资助项目
关键词
芳胺
氰乙基
密度泛函理论
前线轨道
电子光谱
Aromatic amine
Cyanoethy
Density functional theory
Frontier orbital
Electronic spectrum
