Reactions of Laser-Ablated Uranium Atoms with H{sub 2}O in Excess Argon: A Matrix Infrared and Relativistic DFT Investigation of Uranium Oxyhydrides
Laser-ablated U atoms react with H{sub 2}O during condensation in excess argon. Infrared absorptions at 1416.3, 1377.1, and 859.4 cm{sup -1} are assigned to symmetric H-U-H, antisymmetric H-U-H, and U=O stretching vibrations of the primary reaction product H{sub 2}UO. Uranium monoxide, UO, also formed in the reaction, inserts into H{sub 2}O to produce HUO(OH), which absorbs at 1370.5, 834.3, and 575.7 cm{sup -1}. The HUO(OH) uranium(IV) product undergoes ultraviolet photoisomerization to a more stable H{sub 2}UO uranium(VI) molecule, which absorbs at 1406.4 and 885.9 cm{sup -1}. The addition of another water molecule to either HUO(OH) or H{sub 2}UO produces H{sub 2}UO(OH){sub 2}. Several of these species, particularly H{sub 2}UO{sub 2}, appear to form Ar coordinated complexes. The predicted vibrational frequencies, relative absorption intensities, and isotopic shifts from relativistic DFT calculations are in good agreement with observed spectra, which further support the identification of novel uranium oxyhydrides from matrix infrared spectra.
- Research Organization:
- Pacific Northwest National Lab., Richland, WA (US), Environmental Molecular Sciences Laboratory (US)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 15016143
- Report Number(s):
- PNNL-SA-43947; INOCAJ; 9598; KP1301030; TRN: US0502078
- Journal Information:
- Inorganic Chemistry, Vol. 44, Issue 7; Other Information: PBD: 4 Apr 2005; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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