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.
出处
《化学研究》
CAS
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)
