密度泛函理论在分子磁学中的应用

通过对桥联双核铁的磁耦合常数的计算，探讨了密度泛函理论计算条件对计算 结果的影响。基于密度泛函理论下的破损态方法，着重讨论了双核 Fe(III)_2的 d~5-d~5电子通过氧桥的超交换作用。研究发现分子的反铁磁通道主要是Fe(III) d_yz和d_z~2与μ-O的p轨道形成的，具有π*/π*和σ*/σ*特征的超交换通道。

Application of Density Functional Theory in Molecular Magnetism

Based on the density functional theory (DFT) combined with the broken symmetry (BS) approach, the magnetic coupling constant of the oxo-bridged iron (III) dimer Cl_3FeOFeCl_3]~(2-) has been obtained under the various computational conditions in ADF code, including the numerical integration precision parameter, exchange-correlation energy functional and basis sets. The superexchange interactions between d~5- d~5 unpaired electrons were also discussed, and the antiferromagnetic coupling of the title compound was attributed to the superexchange pathway characterized by π~*/π~* and σ~* /σ~* ,. coming from the d_(yz) and d_(z~2) orbitals on Fe(III) ions and p orbital on μ-0 atom.