化学学报 ›› 2004, Vol. 62 ›› Issue (23): 2303-2307. 上一篇    下一篇

研究论文

铜(Ⅱ)氮氧自由基配合物铁磁耦合机理的理论研究

孙友敏, 刘成卜, 王若曦   

  1. 山东大学理论化学研究所, 济南, 250100
  • 投稿日期:2004-02-23 修回日期:2004-08-10 发布日期:2014-02-17
  • 通讯作者: 刘成卜,E-mail:cbliu@sdu.edu.cn;Tel:0531-8361398;Fax:0531-8564464. E-mail:cbliu@sdu.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.20133020,20373033)和山东省自然科学基金(No.Y2002B02)资助项目.

Theoretical Study on Ferromagnetically Coupled Interaction of Copper(Ⅱ)-Imino Nitroxide Radical Compound

SUN You-Min, LIU Cheng-Bu, WANG Ruo-Xi   

  1. Institute of Theoretical Chemistry, Shandong University, Jina 250100
  • Received:2004-02-23 Revised:2004-08-10 Published:2014-02-17

用密度泛函理论结合对称性破损态方法对氮氧双自由基以及铜(Ⅱ)-氮氧自由基配合物的磁耦合常数进行了计算.结果表明铜(Ⅱ)-氮氧自由基配合物为铁磁耦合.对配合物磁轨道进行了分析,表明体系的铁磁耦合作用主要来自于Cu离子的轨道与自由基的π*轨道正交.自旋密度分布分析显示:在氮氧自由基与金属铜两个自旋耦合片的自旋耦合主要来自于中心Cu离子的轨道电子向氮氧自由基上的π*轨道的电子转移,这一电子特征的变化引起的自旋离域在Cu离子和氮氧自由基片的铁磁耦合中起到了重要的作用.

关键词: 氮氧双自由基, 铜(Ⅱ)-氮氧自由基配合物, 铁磁耦合作用, 密度泛函

DFT-BS calculations were performed on the imino nitroxide diradical and copper(Ⅱ)-diradical compound to obtain the J values.The results show that the coupled interaction between imino nitroxide diradical and copper(Ⅱ) is ferromagnetical.The orbital analysis shows that the fairly strong ferromagnetic interaction in copper(Ⅱ)-diradical compound is operative due to the orthogonality of the Cu(Ⅱ) d x2-y2 orbital with imino nitroxide π* orbital.The spin density population shows that the electron transfer takes place from the Cu(Ⅱ) ion to imino nitroxide, which is important in the mechanism of exchange interaction in Cu(Ⅱ)-radical system.

Key words: imino nitroxide biradical, copper(Ⅱ)-imino nitroxide radical complex, ferromagnetically coupled interaction, density functional theory