X-ray photoelectron spectroscopy (XPS) is a widely used technique in material characterization, enabling the acquisition of chemical information by measuring the core-level electron binding energy (BE) of target elements. Theoretical simulations of XPS typically provide a streamlined and condition-free methodology for obtaining material XPS data. However, for iron-based systems, the complex magnetic properties, strong electron–electron correlation interactions, and the absence of standard sample pose a significant challenge to establish an efficient and accurate simulation approach. This work introduces a high-throughput framework designed for the standardization and efficient calculation of the Fe 2p core-level BE shifts. With this framework, the reliability of the theoretical method was comprehensively evaluated, encompassing an all-electron extension of the delta self-consistent field method and orbital energy approximation methods based on the pseudopotential. Furthermore, a series of standard samples of iron compounds were prepared under ultrahigh-vacuum conditions to provide measured XPS values as references to evaluate the theoretical simulations. Through this evaluation, the FSⁿ method with the PBE functional was established as the most suitable for simulating XPS in iron-based materials, demonstrating a remarkable accuracy with an error of merely 0.02 eV. Our methodology offers a standardized approach for the analysis of iron compounds, laying the groundwork for quantitative analysis of more complex systems in future investigations.

中文翻译：

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铁化合物X射线光电子能谱高效准确的理论模拟


X 射线光电子能谱 (XPS) 是材料表征中广泛使用的技术，通过测量目标元素的核心级电子结合能 (BE) 来获取化学信息。 XPS 的理论模拟通常提供一种简化且无条件的方法来获取材料 XPS 数据。然而，对于铁基系统，复杂的磁特性、强的电子-电子相关相互作用以及标准样品的缺乏对建立高效、准确的模拟方法提出了重大挑战。这项工作引入了一个高通量框架，专为 Fe 2p 核心级 BE 位移的标准化和高效计算而设计。在此框架下，综合评估了理论方法的可靠性，包括全电子扩展的δ自洽场方法和基于赝势的轨道能量近似方法。此外，在超高真空条件下制备了一系列铁化合物的标准样品，以提供测量的XPS值作为评估理论模拟的参考。通过此次评估，具有 PBE 泛函的 FS ⁿ 方法被认为是最适合模拟铁基材料 XPS 的方法，显示出极高的精度，误差仅为 0.02 eV。我们的方法为铁化合物的分析提供了标准化方法，为未来研究中更复杂系统的定量分析奠定了基础。