Systematic ab-initio study of the ligand-field spectra of hexacyanometalate complexes
Systematic ab-initio study of the ligand-field spectra of hexacyanometalate complexes
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六氰基金属盐配合物配体场光谱的系统从头算研究
DOI：
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发表时间：
1993
期刊：
影响因子：
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通讯作者：
Bjrn O. Roos
中科院分区：
文献类型：
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作者：
K. Pierloot;E. Praet;L. Vanquickenborne;Bjrn O. Roos
用完全活性空间（CAS）自洽场（SCF）方法和二阶微扰方法（CASPT 2）研究了第一排六氰根配合物V（CN）6 4-，Cr（CN）6 3-，Mn（CN）6 3-，4-，Fe（CN）6 3-，4-和Co（CN）6 3-的基态和配位场激发态.其应用CASSCF波函数作为参考。结果表明，CASSCF波函数可以很好地描述基态和激发态的电子结构，它是基于10个直接参与金属-氰化物键合的轨道的活性空间：主要具有金属3d特征的2 t2 g和6 egg轨道以及它们的配体对应物3 t2 g（CNπ *）和Seg（CNσ）.剩余的相关效应在第二步CASPT 2中处理
The ground and ligand field excited states of the first-row hexacyanometalate complexes V(CN) 6 4- , Cr(CN) 6 3- , Mn(CN) 6 3-,4- , Fe(CN) 6 3-,4- , and Co(CN) 6 3- have been studied using the complete active space (CAS) self-consistent field (SCF) method and a second-order perturbation approach (CASPT2), which applies the CASSCF wave function as a reference. It is shown that the major features of the electronic structure of both the ground state and the excited states are properly described by a CASSCF wave function based on an active space of the 10 orbitals directly involved in the metal-cyanide bonding: the 2t 2g and 6e g orbitals with mainly metal 3d character and their ligand counterparts 3t 2g (CNπ * ) and Se g (CNσ). Remaining correlation effects are dealt with in the second, CASPT2, step