镍和钯两种金属配合物电子结构和光谱性质的理论研究  

A theoretical study on the electronic structures and spectral properties of two Ni(Ⅱ) and Pd(Ⅱ) complexes

作　　者：孙克楠 方磊[1] 何朝政[2] 李永红[1] 

机构地区：[1]河南大学化学化工学院环境与分析科学研究所,河南开封475004 [2]南阳师范学院物理与电子工程学院,河南南阳473061

出　　处：《化学研究》2015年第4期417-421,共5页Chemical Research

基　　金：河南大学省部共建项目(SBGJ090507)

摘　　要：采用密度泛函理论(DFT),在PBE0/6-31+G(d)-LANL2DZ水平下优化了Ni和Pd两种金属配合物A和B的基态几何构型,并在相同水平下进行了频率分析以确认都是实频.利用含时密度泛函理论(TD-DFT)和极化连续介质模型(PCM),在TD-PBE0/6-31+G(d)-LANL2DZ水平下,计算了配合物A和B在二氯甲烷溶剂中的电子结构和吸收光谱.计算结果表明,与中心配位原子Pd相比,Ni较强的配位作用使配合物A具有较小的HOMO-LUMO能级差,从而导致配合物A的最大吸收波长发生红移.Density functional theory（DFT）was employed to optimize the ground-state structures of Ni（Ⅱ）and Pd（Ⅱ）complexes（Aand B）with the specific PBE0 functional and the mixed 6-31＋G（d）-LANL2 DZ basis set.And the frequencies were calculated at the same level to confirm that all optimized geometries show no imaginary frequency.The electronic structures and absorption spectra of the two complexes Aand B were evaluated by using time-dependent density functional theory（TD-DFT）in dichloromethane solvent associated with the polarized continuum model（PCM）at the TD-PBE0/6-31＋G（d）-LANL2 DZ level.The result indicates that the stronger coordination of Ni（Ⅱ）as compared to the Pd（Ⅱ）will decrease the energy gap between HOMO and LUMO for complex A.Consequently,the maximum absorption wavelength of complex Apresents a red shift.

关 键 词：密度泛函理论 吸收光谱 Ni、Pd配合物 二吡咯甲烯 二硫代氨基甲酸盐 

分 类 号：O641.3[理学—物理化学]