NiO 的 Ni 2p XPS 的主要特征和卫星特征,Inorganic Chemistry

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NiO 的 Ni 2p XPS 的主要特征和卫星特征
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-11-02 , DOI: 10.1021/acs.inorgchem.2c02549
Paul S Bagus ₁ , Connie J Nelin ₂ , C Richard Brundle ₃ , B Vincent Crist ₄ , Eugene S Ilton ₅ , Nabajit Lahiri ₅ , Kevin M Rosso ₅

Affiliation

离子化合物中阳离子的复杂主要和卫星 X 射线光电子能谱 (XPS) 特征的起源和分配一直是使用不同方法进行广泛理论研究的主题。人们一致认为，在分子轨道模型中，需要考虑不同类型的构型。具体来说，那些核心电子被移除但没有发生其他构型变化的那些，以及那些除了电离之外，离子构型也有振动或电荷转移变化的。但是，对于将 XPS 功能分配给这些配置存在强烈的分歧。目前的工作旨在基于 NiO 簇模型的从头算分子轨道波函数 (WF) 解决 NiO 的 Ni 2p XPS 的主要和卫星特征的起源。早期离子化合物的从头算 XPS 研究中的一个主要问题是使用一组无法正确描述对完整 XPS 光谱有贡献的所有离子构型的通用轨道。这在目前的工作中通过使用轨道来解决，这些轨道针对有助于 XPS 的不同配置的占用平均值进行了优化。使用状态平均 (SA) 轨道的方法通过不同平均值之间的比较以及通过在离子状态的 WF 中使用高阶激发来验证。₂ O ₃并证明了使用为 SA 优化的轨道获得的 XPS 的不同特征的特征和起源的分配的可靠性和普遍性。_{这些分子轨道方法允许根据振动激发的重要性和 2p 1/2}和 2p _3/2自旋轨道分裂子壳的电离耦合来表征离子态。这项工作为确定主要和卫星 XPS 特征的特征奠定了基础，并指出了它们在材料电子结构中的起源。

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Main and Satellite Features in the Ni 2p XPS of NiO

The origin and assignment of the complex main and satellite X-ray photoelectron spectroscopy (XPS) features of the cations in ionic compounds have been the subject of extensive theoretical studies using different methods. There is agreement that within a molecular orbital model, one needs to take into account different types of configurations. Specifically, those where a core electron is removed, but no other configuration changes are made and those where in addition to ionization, there are also shake or charge-transfer changes to the ionic configuration. However, there are strong disagreements about the assignment of XPS features to these configurations. The present work is directed toward resolving the origin of main and satellite features for the Ni 2p XPS of NiO based on ab initio molecular orbital wave functions (WFs) for a cluster model of NiO. A major problem in earlier ab initio XPS studies of ionic compounds has been the use of a common set of orbitals that was not able to properly describe all the ionic configurations that contribute to the full XPS spectra. This is resolved in the present work by using orbitals that are optimized for averages of the occupations of the different configurations that contribute to the XPS. The approach of using state-averaged (SA) orbitals is validated through comparisons between different averages and through use of higher order excitations in the WFs for the ionic states. It represents a major extension of our earlier work on the main and satellite features of the Fe 2p XPS of Fe₂O₃ and proves the reliability and the generality of the assignments of the character and origin of the different features of the XPS obtained with orbitals optimized for SAs. These molecular orbital methods permit the characterization of the ionic states in terms of the importance of shake excitations and of the coupling of ionization of 2p_1/2 and 2p_3/2 spin–orbit split sub shells. The work lays the foundation for definitive assignments of the character of main and satellite XPS features and points to their origin in the electronic structure of the material.

更新日期：2022-11-02

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