Photoelectrons Are Not Always Quite Free
Photoelectrons Are Not Always Quite Free
复制标题
光电子并不总是完全自由的
DOI：
10.1021/acs.jpclett.8b03253
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Jarrold, Caroline Chick
中科院分区：
文献类型：
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作者：
Mason, Jarrett L.;Topolski, Josey E.;Ewigleben, Joshua;Iyengar, Srinivasan S.;Jarrold, Caroline Chick
在光子能量范围内获得的sm20光电子能谱在相对激发态带强度上表现出异常变化。具体来说，随着光子能量的减少，激发态跃迁强度相对于向中性基态的跃迁而增加，这与阈值效应的预期相反。这一现象在之前的研究中被观察到，用Nd:YAG（2.330和3.495 eV）两种不同的谐波输出收集了几种富含sm的同系和异系镧系氧化物[J]。化学。Phys.2017, 146, 194310]。我们将这些异常强度与基态和激发态阴离子和中性态的种群联系起来，通过在绝热和突然极限内的时间依赖摄动理论的检查，并首次表明光电子能谱中的跃迁强度在测量激发态的参与方面具有深刻的意义。我们相信我们的结果将对其他具有特别高密度可达自旋态的富电子系统的研究具有重要意义。
The photoelectron spectra of Sm2O–obtained over a range of photon energies exhibit anomalous changes in relative excited-state band intensities. Specifically, the excited-state transition intensities increase relative to the transition to the neutral ground state with decreasing photon energy, the opposite of what is expected from threshold effects. This phenomenon was previously observed in studies on several Sm-rich homo- and heterolanthanide oxides collected with two different harmonic outputs of a Nd:YAG (2.330 and 3.495 eV) [J. Chem. Phys.2017,146, 194310]. We relate these anomalous intensities to populations of ground and excited anionic and neutrals states through the inspection of time-dependent perturbation theory within the adiabatic and sudden limits and for the first time show that transition intensities in photoelectron spectroscopy have a deep significance in gauging participation from excited states. We believe our results will have significance in the study of other electron-rich systems that have especially high density of accessible spin states.