铜(Ⅰ)、银(Ⅰ)氮氧自由基配合物磁构效应的理论研究  

THEORETICAL STUDY ON THE MAGNETO-STRUCTURAL CORRELATION FOR Cu (Ⅰ) AND Ag (Ⅰ) IMINO NITROXIDES COMPLEXES

作　　者：黄俭根[1] 周光培[1] 应少明[1] 罗秋燕[1] 

机构地区：[1]井冈山大学化学化工学院,江西吉安343009

出　　处：《井冈山大学学报（自然科学版）》2010年第1期28-35,共8页Journal of Jinggangshan University (Natural Science)

基　　金：江西省教育厅科技项目资助(赣教技字[2006]262号);井冈山大学博士科研启动基金项目

摘　　要：采用密度泛函结合对称性破损(DFT-BS)方法,研究了铜(Ⅰ)、银(Ⅰ)氮氧自由基配合物磁构效应。计算结果表明,在考察改变两个氮氧自由基二面角(θ)而引起磁交换偶合常数(J)的变化时发现,将AgⅠ和CuⅠ配合物中氮氧自由基的正交排列逐渐转为平行排列,最终都实现由铁磁性偶合转变为反铁磁性偶合,但转变的过程并不完全相同。分子轨道和自旋集居数分析都很好解释了计算结果。分析还表明,AgⅠ和CuⅠ两个结构相似的配合物,磁构效应之所以不同,实际上是由它们的磁偶合机理不同所导致。Based on the combined broken-symmetry density functional approach, magneto-structural correlations of [M 1 （imino nitroxide ）2]（PF6）（ M 1 = Ag 1 and Cu 1 ） are discussed by changing the dihedral angle θbetween two imino nitroxide radical planes. The calculated magnetic coupling constant J indicates that the ferromagnetic coupling between imino nitroxides through diamagnetic metal ions （Ag1and Cu1） transform into antimagnetic coupling as the orthogonal arrangement become into the parallel arrangement, but the magneto-structural correlations difference between two complexes is showed in the transform process. The analysis of foregoing molecular orbit and spin density well explain the magneto-structural correlations, the analysis results also indicate that the magneto-structural correlations difference between two complexes, which have similar structure, is due to theirs different magnetism coupling mechanism in fact.

关 键 词：氮氧自由基 磁构效应 密度泛函理论 对称破损态方法 

分 类 号：O641.4[理学—物理化学]