密度泛函理论在分子磁学中的应用1.单氧桥联双核铁(III)[Cl_3FeOFeCl_3]^(2-)磁耦合作用  

Application of Density Functional Theory in Molecular Magnetism 1. Magnetic Coupling Interaction in Oxo-Bridged Iron(III) Dimer [Cl_3FeOFeCl_3]^(2-)

作　　者：任杰[1] 陈志达[1] 

机构地区：[1]北京大学化学与分子工程学院,稀土材料化学及应用国家重点实验室,北京100871

出　　处：《化学学报》2003年第10期1537-1542,共6页Acta Chimica Sinica

基　　金：国家自然科学基金 (Nos .2 0 2 730 0 5;2 0 0 2 30 0 5);国家重点基础研究发展规划基金 (No .G1 9980 6 1 30 5)资助项目

摘　　要：通过对桥联双核铁 (III) [Cl3FeOFeCl3] 2 - 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d5 d5 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)的dyz和dz2 与 μ O的p轨道形成的 ,具有π /π 和σ /σBased on the density functional theory (DFT) combined with th e broken symmetry (BS) approach, the magnetic coupling constant of the oxo-brid ged iron(III) dimer [Cl 3FeOFeCl 3] 2- has been obtained under the var ious computational conditions in ADF code, including the numerical integration p recision parameter, exchange-correlation energy functional and basis sets. The superexchange interactions between d 5-d 5 unpaired electrons were also discu ssed, 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 orbita l on μ-O atom.

关 键 词：密度泛函理论 分子磁学 单氧桥联双核铁(Ⅲ) [Cl3FeOFeCl3]^2- 磁耦合作用 超交换作用 对称性破损方法 

分 类 号：O641[理学—物理化学]