三种席夫碱-Ni(Ⅱ)配合物的电子结构和吸收光谱的理论计算  

Theoretical calculations on the electronic structure and absorption spectra of three kinds of Ni(Ⅱ) complexes with Schiff base ligands

作　　者：李洁琼[1] 赵清岚[1] 

机构地区：[1]河南大学化学化工学院,河南开封475004

出　　处：《化学研究》2014年第5期497-503,共7页Chemical Research

基　　金：河南大学省部共建项目(SBGJ090507)

摘　　要：采用B3LYP/6-31+G(d)-LANL2DZ方法优化了三种Ni(Ⅱ)的席夫碱配合物基态的几何构型,并在相同水平下进行了频率分析以确认稳定点的性质;利用含时密度泛函理论和极化连续介质模型(PCM),按TDB3LYP/6-31+G(d)-LANL2DZ水平计算了目标配合物在N,N-二甲基甲酰胺溶剂中的电子结构和吸收光谱.计算结果表明,配体中间位甲氧基的存在使配合物A具有较大的HOMO-LUMO能级差;且三种Ni(Ⅱ)配合物的S0→S1态的跃迁能按照A→B→C的顺序依次降低.Geometry optimizations and frequency calculations of three Ni（II）metal complexes with tetradentate Schiff base ligands in the ground state were performed at B3LYP/6-31 ＋G （d）-LANL2DZ level,and the characteristics of the stationary points were determined.On the basis of the optimized geometries,the absorption spectra of the three complexes were calculat-ed in N,N-dimethylformamide solvent by using time-dependent density functional theory （TD-DFT）at the TD-B3LYP/6-31＋G（d）-LANL2DZ level in association with the polarized continu-um model （PCM）.Calculation results indicate that the energy gap between the HOMO and LUMO is enlarged because of the existence of m-methoxyl group,which results in the red-shift of the lowest-lying absorption bands of the three Ni（II）complexes in the sequence of A→B→C.

关 键 词：席夫碱 NI(II)配合物 含时密度泛函理论 电子结构 吸收光谱 计算 

分 类 号：O641.3[理学—物理化学]