Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis.
Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis.
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基于多参考波函数分析确定 CH2CeF2 和 OCeF2 的铈氧化态
DOI：
10.1021/acs.jpca.6b03770
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
M. Dolg
中科院分区：
文献类型：
--
作者：
O. Mooßen;M. Dolg
用密度泛函理论(DFT)和基于波函数的从头算方法研究了最近实验研究的分子ZCeF2(Z=CH2，O)的几何和电子结构。特别注意了Ce-Z金属-配位键，特别是Ce4f和Z2p轨道相互作用的性质和由此产生的可能的多组态特征，以及Ce的氧化态的分配反映了电子结构。计算了完整的活动空间自洽场(CASSCF)，然后计算了活动轨道空间的轨道自转。亚甲基化合物CH2CeF2具有开壳单重态基态，在强混合天然CASSCF轨道的基础上表现为两种构型的波函数。如果使用接近纯的Ce4f和C2p轨道，也可以用Ce 4f1C2p1的主要组态来非常简洁地描述该体系。在这些定域轨道的基础上，该分子几乎是单构型的，应该最好地描述为Ce(III)体系。用Ce4f和O2p强混合自然轨道的单组态波函数描述氧OCeF2络合物的单重态基态是闭壳性质的。Ce(IV)/Ce(III)化合物在Ce(IV)和Ce(III)原子上的轨道转换导致了多组态波函数，揭示了混合价Ce(IV)/Ce(III)化合物的特征。此外，通过计算电荷涨落算符和局域自旋算符的期望值，分析了局域活性轨道之间的相互作用。CH2CeF2化合物的Ce4f和C2p轨道相互作用是弱共价的，类似于伸展的氢二聚体中H1s轨道的相互作用。相反，OCeF2的局域活性轨道之间的相互作用具有离子性质。报道了在密度泛函、自洽场、二阶Rayleigh-Schrödinger微扰理论、多参考组态相互作用以及单、双和微扰三重耦合团簇(CCSD(T))水平下的Ce-C和Ce-O伸缩振动频率的计算结果，并与实验红外吸收数据进行了比较。
The geometric and electronic structure of the recently experimentally studied molecules ZCeF2(Z = CH2, O) was investigated by density functional theory (DFT) and wave function-based ab initio methods. Special attention was paid to the Ce–Z metal–ligand bonding, especially to the nature of the interaction between the Ce 4f and the Z 2p orbitals and the possible multiconfigurational character arising from it, as well as to the assignment of an oxidation state of Ce reflecting the electronic structure. Complete active space self-consistent field (CASSCF) calculations were performed, followed by orbital rotations in the active orbital space. The methylene compound CH2CeF2has an open-shell singlet ground state, which is characterized by a two-configurational wave function in the basis of the strongly mixed natural CASSCF orbitals. The system can also be described in a very compact way by the dominant Ce 4f1C 2p1configuration, if nearly pure Ce 4f and C 2p orbitals are used. In the basis of these localized orbitals, the molecule is almost monoconfigurational and should be best described as a Ce(III) system. The singlet ground state of the oxygen OCeF2complex is of closed-shell character when a monoconfigurational wave function with very strongly mixed Ce 4f and O 2p CASSCF natural orbitals is used for the description. The transformation to orbitals localized on the cerium and oxygen atoms leads to a multiconfigurational wave function and reveals characteristics of a mixed valent Ce(IV)/Ce(III) compound. Additionally, the interactions of the localized active orbitals were analyzed by evaluating the expectation values of the charge fluctuation operator and the local spin operator. The Ce 4f and C 2p orbital interaction of the CH2CeF2compound is weakly covalent and resembles the interaction of the H 1s orbitals in a stretched hydrogen dimer. In contrast, the interaction of the localized active orbitals for OCeF2shows ionic character. Calculated vibrational Ce–C and Ce–O stretching frequencies at the DFT, CASSCF, second-order Rayleigh–Schrödinger perturbation theory (RS2C), multireference configuration interaction (MRCI), as well as single, doubles, and perturbative triples coupled cluster (CCSD(T)) level are reported and compared to experimental infrared absorption data in a Ne and Ar matrix.
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