摘要
采用对称性破损态方法结合密度泛函理论,选用典型的强反铁磁双核配合物作为研究对象,通过与实验数据相比较,探讨了不同密度泛函方法与基组对计算铜配合物[Cu2(mMP)4(H2O)2]·H2O交换耦合常数的准确度.结果表明,4种混合密度泛函DFT(B3LYP,B3P86,B3PW91和PBE0)的计算结果都能和实验所观察到的值-324cm-1符号一致,但B3PW91方法得到的结果和实验结果吻合程度最好,同时采用方法B3PW91方法计算所得的交换耦合常数Jab对基组的依赖性较大.研究表明,2个Cu(Ⅱ)离子之间的反铁磁相互作用主要源于单占据分子轨道SOMOs大的能量劈裂和桥联配体O-C-O轨道的重叠.
In the present work,the magnetic properties of antiferromagnetic complex [Cu2（mMP）4（H2O）2]·H2O has been investigated on the basis of various unrestricted density functional theory（DFT）with the broken symmetry（BS）approach.The computational results of the hybrid density functional theory（B3LYP,B3P86,B3PW91 and PBE0）is well agreement with the negative sign of the experimental value,the result of B3PW91calculation method is closer to the experimental one.The B3PW91 calculation method has a large dependent on the basis set.To the dinuclear copper coordination complex,B3PW91/LANL2DZ have a significant improvement in exchange coupling constants with the experimental data.
出处
《分子科学学报》
CAS
CSCD
北大核心
2014年第3期252-255,共4页
Journal of Molecular Science
基金
黑龙江省教育厅项目(12531722)
