氧桥联希夫碱GdNi双核配合物磁学性质理论研究

The Magnetic properties of the Oxygen atoms Bridged Schiff Base Dinuclear Gd~ⅢNi~Ⅱ Complexes: Theoretical Studies

采用密度泛函理论结合对称性破损态方法,选择四类方法和不同基组对氧桥联希夫碱Gd~ⅢNi~Ⅱ双核配合物[Ni(HL)(H_2O)(tfa)Gd(hfac)_2]磁学性质进行研究。结果表明,在PW91/TZVP(Gd为SARC2-DKH-QZVP)水平下计算的数值与实验值最吻合。分子磁轨道分析显示,分子磁轨道主要由顺磁中心Gd(1)的4f轨道、顺磁中心Ni(2)的3d_(xz)与3d_(x^2-y^2)轨道、席夫碱配体提供的桥联配位O原子和三氟乙酸根离子提供的桥联配位O原子的p轨道组成。自旋布居分析表明,Gd(1)以自旋极化为主,Ni(2)以自旋离域为主。

The magnetic coupling constant of the binuclear GdIII Ni II complex[Ni(HL)(H2O)(tfa)Gd(hfac)2]were calculated using DFT-BS by several DFT methods and basis sets.The calculated values at the PW91/TZVP(Gd/SARC2-DKH-QZVP)level showed an excellent agreement with the experimental data.The analysis of magnetic orbital showed that molecule magnetic orbitals are composed of the 4f orbitals of Gd atom the 3dx2-y2 orbits and 3dxz orbitals of the Ni atom and the p orbits of O atoms with trifluoroacetate ion and Schiff base bridged.The data of spin density indicated that the spin polarization from Gd(1)and spin delocalization from Ni(2).