Bridging Electron Density Relaxation and XPS Spectroscopy: Orbital-Resolved Trends in Core-Ionized Aum (m = 4, 10, 20) and (TiO2)n (n = 2–4) Clusters

IF 3 2区化学 Q3 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry A Pub Date : 2026-09-10 Epub Date: 2026-08-28 DOI:10.1021/acs.jpca.6c01107

Bartłomiej Gostyński

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Abstract

Core electron binding energies (CEBEs) in nanomaterials encode element-specific chemical information, yet their interpretation is often complicated by quantum size effects and site-to-site heterogeneity in small finite systems. Here, I use all-electron Δ-Self Consistent Field (ΔSCF) density functional theory to quantify site-resolved CEBEs and the accompanying orbital-level relaxation response in two chemically distinct cluster families: metallic Au_m (m = 4, 10, 20) and anatase-like (TiO₂)_n (n = 2–4), including multiple structural isomers. Beyond total-energy differences, I analyze the orbital-resolved Kohn–Sham eigenvalue shift, Δε, induced by a localized core–hole. Finally, I assess a summed eigenvalue-shift descriptor, ΣΔε, as a compact reduction of these data. The results highlight the intrinsically quantum-mechanical origin of core-level shifts in finite systems and suggest that orbital-resolved relaxation patterns may serve as auxiliary, physically interpretable descriptors in future core-level spectroscopy studies.

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桥接电子密度弛豫和XPS光谱：核电离Aum （m = 4,10,20）和（TiO2）n （n = 2-4）团簇的轨道分辨趋势

纳米材料中的核心电子结合能（CEBEs）传递了特定元素的化学信息，但在小型有限系统中，它们的解释往往因量子尺寸效应和点对点的异质性而变得复杂。在这里，我使用全电子Δ-Self ConsistentField （ΔSCF）密度泛函数理论来量化两个化学上不同的簇族：金属Aum （m = 4,10,20）和尖钛矿样（TiO2）n (n = 2-4)，包括多个结构异构体的位点解析cebe和伴随的轨道能级弛豫响应。除了总能量差异之外，我还分析了由局部核洞引起的轨道分辨的Kohn-Sham特征值移位Δε。最后，我评估一个求和的特征值移位描述符ΣΔε，作为这些数据的紧凑约简。这些结果强调了有限系统中核能级位移的内在量子力学起源，并表明轨道分辨弛豫模式可能在未来的核能级光谱研究中作为辅助的、物理上可解释的描述符。

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来源期刊

The Journal of Physical Chemistry A 化学-物理：原子、分子和化学物理

CiteScore

5.20

自引率

10.30%

发文量

922

审稿时长

1.3 months

期刊介绍： The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.