具有三维结构的Co(II)配合物二阶非线性光学性质的DFT研究.pdfVIP

理化学学报(Wuli Huaxue Xuebao) 836 Acta Phys. Chim. Sin., 2006, 22(7) ：836 839 July [Article] 具有三维结构的Co(II)配合物二阶非线性光学性质的DFT 研究 永清 刘春光 陈 徽 苏忠民 杨国春 王荣顺 (东北师范大学化学学院, 功能材料化学研究所, 长春 130024) 摘要 以实验合成出的Schiff 碱配体和Co(II)配合物为母体, 设计了Schiff 碱配体和具有三维结构的Co(II)配 合 . 采用密度泛函理论的B3LYP/6鄄31g(d)鄄FF 方法对具有开壳层电子组态Co(II)配合物及相应配体的二阶非 线性光学(NLO)效应进行了计算. 结果表明: Schiff 碱配体形成配合物后分子的二阶NLO 性质没有发生大的改 变, 这是由于金属Co2+离子在配合物电荷转移(CT)过程中起到了桥的作用, 对分子的二阶NLO 响应直接贡献不 大. 结合配合物的前线分子轨道分析发现, 在分子内电荷转移过程中, 对分子二阶NLO 系数的主要贡献是配体 内电荷转移(ILCT)跃迁. 关键词： Co(II)配合 , Schiff 碱配体, 非线性光学系数, 密度泛函理论(DFT) 中图分类号： O641 DFT Study on Second order Nonlinear Optical Properties of a Series of Three dimensional Cobalt(II) Metal Complexes QIU, Yong鄄Qing LIU, Chun鄄Guang CHEN, Hui SU, Zhong鄄Min YANG, Guo鄄Chun WANG, Rong鄄Shun (Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China) Abstract For designing three鄄dimensional cobalt (II) metal complexes and Schiff base ligands, the geometry was taken from the starting structures based on the crystallographic data . The density functional theory (DFT) B3LYP/ 6鄄31g(d)鄄FF method was used to calculate the second鄄order nonlinear optical (NLO) properties of open鄄shell cobalt(II) metal complexes. The key finding revealed that when compared with the Schiff base ligands, the second鄄order NLO properties of the metal complexes do not change obviously , the reason being that the NLO response