期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 120, 期 7, 页码 1084-1096出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b11354
关键词
-
资金
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0006979]
- U.S. Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory
- U.S. Department of Energy (DOE) [DE-SC0006979] Funding Source: U.S. Department of Energy (DOE)
Uranium oxide clusters UOx- (x = 3-5) were produced by laser vaporization and characterized by photoelectron spectroscopy and quantum theory. Photoelectron spectra were obtained for UOx- at various photon energies with well-resolved detachment transitions and vibrational resolution for x = 3 and 4. The electron affinities of UOx 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 UOx 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 eta(1)- or eta(2)-bonded O-2 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.
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