物理化学学报 >> 2003, Vol. 19 >> Issue (06): 549-552.doi: 10.3866/PKU.WHXB20030614

研究论文 上一篇    下一篇

酚氧桥联铜钴异双核配合物的密度泛函研究

张敬来;苗体方;陶偌偈;臧双全;田安民   

  1. 河南大学化学化工学院,开封 475001;四川大学化学系,成都 610064
  • 收稿日期:2002-10-21 修回日期:2003-01-15 发布日期:2003-06-15
  • 通讯作者: 张敬来 E-mail:zhangjinglai@henu.edu.cn

Density Functional Theory Study on Phenolato-bridged CuⅡ-CoⅡ Heterobinuclear Complex

Zhang Jing-Lai;Miao Ti-Fang;Tao Ruo-Jie;Zang Shuang-Quan;Tian An-Min   

  1. Chemistry and Chemical Engineering College of Henan University,Kaifeng 475001; Deparment of Chemistry,Sichuan University,Chengdu 610064
  • Received:2002-10-21 Revised:2003-01-15 Published:2003-06-15
  • Contact: Zhang Jing-Lai E-mail:zhangjinglai@henu.edu.cn

摘要: 用密度泛函方法,在ROB3LYP/SDD//ROB3LYP/LanL2MB水平上,对酚氧桥联CuⅡ-CoⅡ异双核配合物CuCo(TS)(H2O),进行了理论计算.优化得到了它的单、三重态的平衡几何构型,计算了它们的谐振动频率.结果表明,该配合物分子的三重态比单重态稳定;电子自旋布居高度集中在Co(6)及其周围的配体原子上,而Cu(1)则没有发现电子自旋布居; 体系中存在较强的自旋离域效应.体系的前线分子轨道主要由Co(6)的d轨道和配体原子的p轨道组成,这有利于配体原子与Co(6)之间的电子转移.计算结果与实验符合得很好.

关键词: 异双核配合物, 密度泛函, 自旋布居, 分子磁性

Abstract: The phenolato-bridged CuⅡ-CoⅡ heterobinuclear complex ,CuCo(TS)(H2O) has been studied with density functional theory(DFT) calculations at ROB3LYP/SDD//ROB3LYP/LanL2MB level ,the equilibrium geometries in singlet and triplet configurations of the complex were optimized and the harmonic vibrational frequencies were calculated .The results show that the triplet electronic configuration of the complex is more stable than the singlet one.The spin populations of electrons are predominantly located on the Co(6) atom and its neighbours,no population is found on the Cu(1) atom.There is a strong effect of spin delocalization in the complex.The frontier orbits are mainly composed of d-like orbits of Co(6)atom and p-like orbits of the ligand.The frontier orbits of this constitution favors the electron transfer between Co(6)atom and the ligand.These results are in good agreement with the results obtained from experiment.

Key words: Heterobinuclear complex, Density functional theory, Spin population,  Molecular magnetism