铁磁性EE叠氮桥联双核铜配合物磁学性质理论研究  

Magnetic Properties of Ferromagnetic Binuclear Cu(Ⅱ) Complex with End-to-end Azido Bridging Ligands: Density Functional Theory Studies

作　　者：王昌来 罗树常 李宏媛 夏维银 张志 Wang Changlai;Luo Shuchang;Li Hongyuan;Xia Weiyin;Zhang Zhi(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)

机构地区：[1]贵州工程应用技术学院化学工程学院,贵州毕节551700 [2]贵州省化学化工实验教学示范中心,贵州毕节551700

出　　处：《山东化工》2018年第5期26-28,30,共4页Shandong Chemical Industry

基　　金：贵州省教育厅青年科技人才成长项目(黔教合KY字[2017]292);国家级大学生创新创业训练计划项目(201710668009);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);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

摘　　要：采用密度泛函理论结合对称性破损态方法,选择局域密度近似、广义梯度近似、混合泛函、meta-GGA四类方法和不同基组计算铁磁性μ_2-1,3 N_3叠氮桥联配合物[Cu_2(L2)_2(μ_2-1,3-N_3)_2(Cl O_4)_2]磁耦合常数。结果表明,在TPSS0/def2-TZVP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Cu(1)、Cu(2)的3d_(z2)轨道、3d_(xz)轨道、桥联配体N_3^-中N原子的p组成。自旋布居分析表明,顺磁中心Cu(1)、Cu(2)间相互作用以自旋离域为主。The magnetic coupling constant of the ferromagnetic complex[Cu 2(L2)2(μ2-1,3-N 3)2(ClO 4)2]were calculated using DFT-BS by several DFT methods(LDA,GGA,HDFT,meta-GGA)and basis sets.The calculated values at the TPSS0/def2-TZVP level showed an excellent agreement with the experimental data.The analysis of magnetic orbital showed that molecule magnetic orbitals are composed of the 3d z 2 orbits and 3d xz orbitals of the Cu atoms and the p orbits of N atoms with azide ions bridged.The data of spin density indicated that the spin delocalization effects are predominant for the exchange interaction between Cu(1)and Cu(2).

关 键 词：DFT-BS EE叠氮桥 叠氮铜配合物 铁磁性 磁耦合常数 

分 类 号：O641.4[理学—物理化学]