氢键桥联双核铜配合物磁耦合的密度泛函研究  

Density Functional Study of Magnetic Coupling Interaction in Dimeric Copper(Ⅱ) Complex with Hydrogen-bonded Bridges

作　　者：孙友敏[1] 王若曦[1] 刘成卜[1] 

机构地区：[1]山东大学理论化学研究所,济南250100

出　　处：《高等学校化学学报》2005年第2期294-298,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 0 13 3 0 2 0 ;2 0 3 73 0 3 3 );山东省自然科学基金 (批准号 :Y2 0 0 2 B0 2 )资助

摘　　要：在密度泛函理论的基础上 ,应用对称性破损方法研究了氢键桥联双核铜模型配合物的磁耦合行为以及磁耦合常数随 O_ O距离的变化趋势 .计算结果表明 ,反铁磁耦合作用来源于 Cu原子的 dx2 - y2 和氧原子的 px 或 py 磁轨道的部分重叠 ,而 H原子不参与磁耦合作用 .磁耦合常数 J与 O_ O距离 r之间存在指数关系 ,而不是线性关系 .Based on the density functional theory(DFT) combined with the broken symmetry(BS) approach, the magnetic coupling interaction in the hydrogen-bonded copper(Ⅱ) dimmer and the change of magnetic coupling constant with the change of the O_O distance were studied. The orbital analysis shows that the superexchange interaction in the hydrogen-bonded Cu(Ⅱ) dimmers comes from the overlap between the d_ x2-y2 orbital on Cu(Ⅱ) ions and p_x or p_y orbitals on O atoms, whereas the hydrogen bridges do not participate the magnetic coupling. The dependence of the magnetic coupling constant J value on the \{O_O\} distance can be expressed as an exponential function.

关 键 词：对称性破损方法 密度泛函理论 氢键桥联铜二聚体 磁-结构关联 

分 类 号：O-641[理学]