重新审视CeO阴离子光电子能谱：解决卫星跃迁的归属与光脱附机制
Revisiting the CeO Anion Photoelectron Spectrum: Resolving the Assignment and Photodetachment Mechanism of Satellite Transitions
AI总结：
本研究结合高分辨阴离子光电子能谱与多参考相对论计算，重新解析了CeO-光电子能谱，提出了卫星跃迁的暂定归属，并揭示了光脱附机制，强调了理论-实验结合对复杂镧系体系的重要性。
AI中文摘要：
CeO是理解镧系氧化物中电子关联、自旋-轨道耦合以及4f/5d构型混合相互作用的重要模型体系。其阴离子光电子能谱展现出密集的电子流形和多电子shake-up过程，这些因素使光谱归属和光脱附动力学变得复杂。在本研究中，我们将高分辨阴离子光电子能谱与无自旋及自旋-轨道耦合的CASSCF+NEVPT2计算相结合，以表征CeO-和CeO的电子结构。基于分箱的数据分析方法使我们能够观察到被光谱拥挤所掩盖的弱跃迁，而多参考计算则重现了低激发电子结构和脱附能量学。在此基础上，我们为观测到的光电子特征提出了暂定归属。对光脱附选择定则、光电子角分布以及多电子脱附通道的分析，为光谱背后的机制提供了额外见解。这些结果建立了对CeO-光电子能谱的全面解释，并强调了将高分辨光谱学与多参考相对论理论相结合对于电子结构复杂的镧系体系的重要性。
英文摘要：
CeO serves as an important model system for understanding the interplay of electron correlation, spin-orbit coupling, and 4f/5d configurational mixing in lanthanide oxides. Its anion photoelectron spectrum exhibits dense electronic manifolds and multielectron shake-up processes that complicate spectral assignments and photodetachment dynamics. Here, we combine high-resolution anion photoelectron spectroscopy with spin-free and spin-orbit-coupled CASSCF+NEVPT2 calculations to characterize the electronic structure of CeO- and CeO. A binning-based data analysis approach enables observation of weak transitions hidden by spectral congestion, while multireference calculations reproduce the low-lying electronic structure and detachment energetics. On this basis, tentative assignments are proposed for the observed photoelectron features. Analysis of photodetachment selection rules, photoelectron angular distributions, and multielectron detachment channels provides additional insight into the mechanisms underlying the spectrum. These results establish a comprehensive interpretation of the CeO- photoelectron spectrum and underscore the importance of combining high-resolution spectroscopy with multireference relativistic theory for electronically complex lanthanide systems.
