Probing the Electronic Structure and Chemical Bonding of Mono-Uranium Oxides with Different Oxidation States: UOx‿/sup> and UOx (x = 3‿)

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• 作者：Jing Su ; Wei-Li Li ; Gary V. Lopez ; Tian Jian ; Guo-Jin Cao ; Wan-Lu Li ; W. H. Eugen Schwarz ; Lai-Sheng Wang ; Jun Li
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：February 25, 2016
• 年：2016
• 卷：120
• 期：7
• 页码：1084-1096
• 全文大小：546K
• ISSN：1520-5215

文摘

Uranium oxide clusters UO_x^– (x = 3–5) were produced by laser vaporization and characterized by photoelectron spectroscopy and quantum theory. Photoelectron spectra were obtained for UO_x^– at various photon energies with well-resolved detachment transitions and vibrational resolution for x = 3 and 4. The electron affinities of UO_x were measured as 1.12, 3.60, and 4.02 eV for x = 3, 4, and 5, respectively. The geometric and electronic structures of both the anions and the corresponding neutrals were investigated by quasi-relativistic electron-correlation quantum theory to interpret the photoelectron spectra and to provide insight into their chemical bonding. For UO_x clusters with x ≤ 3, the O atoms appear as divalent closed-shell anions around the U atom, which is in various oxidation states from U^II(fds)⁴ in UO to U^VI(fds)⁰ in UO₃. For x > 3, there are no longer sufficient valence electrons from the U atom to fill the O(2p) shell, resulting in fractionally charged and multicenter delocalized valence states for the O ligands as well as η¹- or η²-bonded O₂ units, with unusual spin couplings and complicated electron correlations in the unfilled poly oxo shell. The present work expands our understanding of both the bonding capacities of actinide elements with extended spdf valence shells as well as the multitude of oxygen’s charge and bonding states.