New Photoelectron–Valence Electron Interactions Evident in the Photoelectron Spectrum of Gd 2 O –
New Photoelectron–Valence Electron Interactions Evident in the Photoelectron Spectrum of Gd 2 O –
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Gd 2 O 光电子能谱中明显的新光电子 — 价电子相互作用 —
DOI：
10.1021/acs.jpca.1c07818
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发表时间：
2021
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.;Harb, Hassan;Abou Taka, Ali;Huizenga, Caleb D.;Corzo, Hector H.;Hratchian, Hrant P.;Jarrold, Caroline Chick
在几个镧系低氧化物簇的阴离子光电子（PE）光谱中观察到强光电子-价电子（PEVE）相互作用的证据，从电子结构的角度来看，这些簇异常复杂，并且是强相关系统。 Gd2O– 的 PE 能谱由于其半填充的 4f 子壳层而应具有相对简单的电子结构，表现出大量的电子跃迁。从光谱测定的电子亲和势为0.26 eV。相对于具有较低光子能量的较低能态，向激发态的跃迁强度增加，这与由时间相关的电子-中性相互作用驱动的震动跃迁一致。一组位于 0.7 和 2.3 eV 电子结合能之间的强烈光谱特征被分配给涉及电子从具有大量 Gd 6s 贡献的外价 σu 和 σ 轨道脱离的跃迁。光谱总体上显示出平行的跃迁流形，这与这些轨道的分离是一致的。然而，在几个垂直过渡附近观察到几个不同的垂直过渡。提出了一种可能的解释，即喷射电子与高自旋中性子之间的相互作用。具体来说，从 σu 或 σgorbitals 射出的电子角动量（即 = 1）可以切换到 = 0, 2，并且残余中性点的 Ms 发生相关变化，这是自由电子与中性点自旋之间的自旋轨道耦合。
Evidence of strong photoelectron–valence electron (PEVE) interactions has been observed in the anion photoelectron (PE) spectra of several lanthanide suboxide clusters, which are exceptionally complex from an electronic structure standpoint and are strongly correlated systems. The PE spectrum of Gd2O–, which should have relatively simple electronic structure because of its half-filled 4f subshell, exhibits numerous electronic transitions. The electron affinity determined from the spectrum is 0.26 eV. The intensities of transitions to excited states increase relative to the lower-energy states with lower photon energy, which is consistent with shakeup transitions driven by time-dependent electron–neutral interactions. A group of intense spectral features that lie between electron binding energies of 0.7 and 2.3 eV are assigned to transitions involving detachment of an electron from outer-valence σuand σgorbitals that have large Gd 6s contributions. The spectra show parallel transition manifolds in general, which is consistent with detachment from these orbitals. However, several distinct perpendicular transitions are observed adjacent to several of the vertical transitions. A possible explanation invoking interaction between the ejected electron and the high-spin neutral is proposed. Specifically, the angular momentum of electrons ejected from σuor σgorbitals, which is= 1, can switch to= 0, 2 with an associated change in the Msof the remnant neutral, which is spin–orbit coupling between a free electron and the spin of a neutral.