Ab initio calculation for magnetostructural characterization of azido-bridged Cu(II) dimers

作者：Xiang SC^*; Li JQ; Zhang YF; Zhou LX

来源：Acta Chimica Sinica, 2001, 59(2): 173-178.

• broken symmetry approach
• azido-bridged Cu (II) dimers
• DFT
• magneto-structural

On basis of the broken symmetry approach and density functional theory (DFT), the magnetostructural characterization of azido - bridged Cu ( II) dimers is studied which have end - to - end (EE) and end - on (EO) two main coordination modes. The calculating results show that EE mode gives antiferromagnetic interaction, whereas EO mode gives ferromagnetic coupling in which theta is about 91 degrees - 107 degrees, basically agreealde with the experimental value 96 degrees - 104 degrees. The essence of the magnetostructural characterization lies in d- p- d three centers sigma antibonding action between two Cu d, orbitals and bridged N p(x) orbital in SOMO b(Ig). In the theta region of 95 degrees - 110 degrees the sigma antibonding overlap has the maximum, which leads to the maximum ferromagnetic coupling. It is also shown that tau has no great influence on J, whereas J decreases linearly with increasing r(Cu - N mu).

• 出版日期2001
• 单位福州大学