摘要
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).
作者
范光鼎
罗树常
殷俊
李晓青
方春平
Fan Guangding;Luo Shuchang;Yin Jun;Li Xiaoqing;Fang Chunping(School of Chemical Engineering,Guizhou University of Engineering Science,Bijie 551700,China;The Experiment Education Model Center of the Chemistry and Chemical Engineering of Guizhou Provience,Bijie 551700,China)
出处
《山东化工》
CAS
2018年第6期19-23,共5页
Shandong Chemical Industry
基金
贵州省科技厅
毕节市科技局
贵州工程应用技术学院联合基金(黔科合LH字[2015]7588号
黔科合LH字[2017]7013号)
国家级大学生创新创业训练计划项目(201710668011)
贵州省教育厅青年科技人才成长项目(黔教合KY字[2017]292)
贵州省科技厅联合基金(黔科合J字LKB[2013]19)
贵州省化学工程与技术重点支持学科(黔学位合字ZDXK[2015]32号)
贵州省应用化学特色重点学科
