Acta Chimica Sinica ›› 2004, Vol. 62 ›› Issue (20): 1973-1980.     Next Articles

密度泛函理论在分子磁学中的应用2.混合桥联三核镍配合物自旋交换作用

胡宗超1,2, 卫海燕1, 王凡1, 赵琦华1,3, 陈志达1   

  1. 1. 北京大学化学与分子工程学院, 稀土材料化学及应用国家重点实验室, 北京, 100871;
    2. 贵州大学化学系, 贵阳, 550025;
    3. 云南大学化学系, 昆明, 650091
  • 收稿日期:2004-04-16 修回日期:2004-06-25 出版日期:2004-10-28 发布日期:2014-02-17
  • 通讯作者: 陈志达,E-mail:zdchen@pku.edu.cn E-mail:zdchen@pku.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.20273005,20318001)、教育部博士点基金(No.20030001066)资助项目.

Application of Density Functional Theory to Molecular Magnetism 2. Magnetic Coupling Interaction in Mixed Bridged Trinuclear Nickel Complexes

HU Zhong-Cao1,2, WEI Hai-Yan1, WANG Fan1, ZHAO Qi-Hua1,3, CHEN Zhi-Da1   

  1. 1. Department of Chemistry, State Key Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871;
    2. Department of Chemistry, Guizhou University, Guiyang 550025;
    3. Department of Chemistry, Yunnan University, Kunming 650091
  • Received:2004-04-16 Revised:2004-06-25 Online:2004-10-28 Published:2014-02-17

Calculations on the magnetic coupling interaction in the mixed bridged trinuclear nickel complexes with triazole and isothiocyanate bridge ligands have been carried out by using the density functional theory combined with the broken symmetry approach (DFT-BS). It is found that in the title complexes the coupling interaction of the triazole bridge is antiferromagnetic while the isothiocyanate bridge transfers a ferromagnetic coupling. As increasing the number of isothiocyanate bridge the ferromagnetic characteristic is enhanced. The Mulliken population analyses show that in the title complexes there is a spin delocalization mechanism of magnetic coupling through the bridges. From molecular magnetic orbitals, it is shown that there is a stronger orbital interaction among the local magnetic orbitals through the triazole bridge, while isothiocyanate bridge gives rise to a weaker orbital interaction among the local magnetic orbitals. It is important to note that the DFT-BS suitable to the transition metal binuclear complexes can be also applied to magnetic exchange interaction for the transition metal trinuclear complexes.

Key words: density functional theory, broken symmetry approach, molecular magnetism, superexchange interaction, trinuclear nickel complex