CeO <sub>2中</sub>的电子结构和化学键的性质<sub></sub>,Physical Chemistry Chemical Physics

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CeO _2中的电子结构和化学键的性质
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-06-01 00:00:00 , DOI: 10.1039/c8cp01442f
Konstantin I. Maslakov _{1,

2,

3,

4} , Yury A. Teterin _{1,

2,

3,

4,

5} , Mikhail V. Ryzhkov _{4,

6,

7,

8} , Aleksej J. Popel _{9,

10,

11,

12} , Anton Yu. Teterin _{3,

4,

5} , Kirill E. Ivanov _{3,

4,

5} , Stepan N. Kalmykov _{1,

2,

3,

4,

5} , Vladimir G. Petrov _{1,

2,

3,

4} , Peter K. Petrov _{12,

13,

14,

15} , Ian Farnan _{9,

10,

11,

12}

Affiliation

分析了CeO ₂价电子在0到〜50 eV的结合能范围内的X射线光电子能谱结构。考虑了CeO ₈和Ce ₆₃ O ₂₁₆团簇的核心电子光谱结构参数和相对论离散变分计算结果。化合价和核心电子光谱结构的比较表明，内价（IVMO）和外价（OVMO）分子轨道的形成比多体过程对光谱结构的贡献更大。建立了Ce 4f电子以直接参与CeO _2中的化学键形成失去部分f角色。发现它们主要定位在外价带内。铈5p原子轨道显示参与内和外价分子轨道（MOs）的形成。在IVMO形成大部分采取的是填充铈5P _1/2，5P _3/2和O 2S原子壳，而铈5S电子在化学键形成弱参与。建立了在0到〜50 eV的结合能范围内分子轨道的组成和顺序。建立了CeO ₂分子轨道的定量方案。该方案对于理解化学键的性质以及解释CeO ₂的其他X射线光谱至关重要。评估显示，IVMO电子使OVMO电子形成的化学键减弱了37％。

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The electronic structure and the nature of the chemical bond in CeO2

The X-ray photoelectron spectral structure of CeO₂ valence electrons in the binding energy range of 0 to ∼50 eV was analyzed. The core-electron spectral structure parameters and the results of relativistic discrete-variational calculations of CeO₈ and Ce₆₃O₂₁₆ clusters were taken into account. Comparison of the valence and the core-electron spectral structures showed that the formation of the inner (IVMO) and the outer (OVMO) valence molecular orbitals contributes to the spectral structure more than the many-body processes. The Ce 4f electrons were established to participate directly in chemical bond formation in CeO₂ losing partially their f character. They were found to be localized mostly within the outer valence band. The Ce 5p atomic orbitals were shown to participate in the formation of both the inner and the outer valence molecular orbitals (MOs). A large part in the IVMO formation is taken by the filled Ce 5p_1/2, 5p_3/2 and O 2s atomic shells, while the Ce 5s electrons participate weakly in the chemical bond formation. The composition and the sequent order of the molecular orbitals in the binding energy range of 0 to ∼50 eV were established. A quantitative scheme for the molecular orbitals of CeO₂ was built. This scheme is fundamental for understanding the nature of chemical bonding and also for the interpretation of other X-ray spectra of CeO₂. Evaluations revealed that the IVMO electrons weaken the chemical bond formed by the OVMO electrons by 37%.

更新日期：2018-06-01

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