Mason Jarrett L, Harb Hassan, Abou Taka Ali, Huizenga Caleb D, Corzo Hector H, Hratchian Hrant P, Jarrold Caroline Chick
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
Department of Chemistry and Biochemistry, University of California, Merced, 5200 North Lake Road, Merced, California 95343, United States.
J Phys Chem A. 2021 Nov 18;125(45):9892-9903. doi: 10.1021/acs.jpca.1c07818. Epub 2021 Nov 3.
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 GdO, 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 σ and σ orbitals 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 σ or σ orbitals, which is = 1, can switch to = 0, 2 with an associated change in the M of the remnant neutral, which is spin-orbit coupling between a free electron and the spin of a neutral.
在几种低价镧系元素氧化物团簇的阴离子光电子能谱中观察到了强光电子-价电子（PEVE）相互作用的证据，从电子结构的角度来看，这些团簇异常复杂，并且是强关联体系。由于其4f亚壳层半充满，GdO的光电子能谱应该具有相对简单的电子结构，但却表现出众多的电子跃迁。从该能谱确定的电子亲和能为0.26 eV。随着光子能量降低，向激发态跃迁的强度相对于较低能量态增加，这与由时间相关的电子-中性相互作用驱动的振激跃迁一致。一组位于0.7至2.3 eV电子结合能之间的强光谱特征被归因于涉及从具有大Gd 6s贡献的外层价σ和σ轨道上脱离一个电子的跃迁。总体而言，光谱显示出平行的跃迁流形，这与从这些轨道上的脱离是一致的。然而，在几个垂直跃迁附近观察到了几个明显的垂直跃迁。提出了一种可能的解释，即涉及出射电子与高自旋中性粒子之间的相互作用。具体而言，从σ或σ轨道出射的电子的角动量（ = 1）可以转变为 = 0、2，同时残余中性粒子的M发生相关变化，这是自由电子与中性粒子自旋之间的自旋-轨道耦合。
