Journal of Molecular Spectroscopy ( IF 1.4 ) Pub Date : 2021-06-11 , DOI: 10.1016/j.jms.2021.111496 Mary Marshall , Zhaoguo Zhu , Junzi Liu , Kit H. Bowen , Lan Cheng
A joint relativistic coupled-cluster and experimental photoelectron (PE) spectroscopic study of the uranyl dichloride anion, UOCl, is reported. Sophisticated electronic-structure calculations predict the photodetachment of UOCl to involve a U 5f electron and to be followed by significant geometry relaxation. Therefore, the adiabatic electron affinity (EA) of the uranyl dichloride neutral molecule, UOCl, and the vertical detachment energy (VDE) of its anion, UOCl, provide valuable information about its uranium 5f orbital energies. The EA value was computed to be 3.15 eV. The VDE value was calculated to be 3.55 eV by augmenting the computed EA with a shift derived from a Franck–Condon simulation using coupled-cluster potential energy surfaces. The VDE, which corresponds to the highest intensity peak in the PE spectrum, was measured to be 3.69 ± 0.20 eV, in good agreement with the computed value. The origin transition in the PE spectrum, whose electron binding energy corresponds to the EA, was assigned to the feature at 3.2 ± 0.20 eV, consistent with the computed EA.
中文翻译:
二氯化铀阴离子 UO 的阴离子光电子光谱和相对论耦合簇研究氯
二氯化铀阴离子 UO 的联合相对论耦合簇和实验光电子 (PE) 光谱研究氯, 报道。复杂的电子结构计算预测 UO 的光分离氯涉及 U 5f 电子,然后是显着的几何弛豫。因此,绝热电子亲和势(EA) 的二氯化铀中性分子,UO氯,以及其阴离子的垂直分离能 (VDE),UO氯,提供有关其铀 5f 轨道能量的宝贵信息。EA值计算为 3.15 eV。通过增加计算的 EA,VDE 值计算为 3.55 eV使用耦合簇势能面从 Franck-Condon 模拟得出的偏移。对应于 PE 光谱中最高强度峰值的 VDE 测量值为 3.69 ± 0.20 eV,与计算值非常一致。PE 光谱中的原点跃迁,其电子结合能对应于 EA, 被分配到 3.2 ± 0.20 eV 的特征,与计算的 EA 一致.