A Uranyl Peroxide Dimer in the Gas Phase
Abstract
For this study, the gas-phase uranyl peroxide dimer, [(UO2)2(O2)(L)2]2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO22+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO2)2(O)(L)2]2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO2)2(OH)2(L)2]2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide of particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO2)2(O2)(L)2]2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO2)2(O2)]2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite andmore »
- Authors:
-
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- European Commission, Karlsruhe (Germany). Joint Research Centre
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1436151
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 7; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY
Citation Formats
Dau, Phuong D., Dau, Phuong V., Rao, Linfeng, Kovacs, Attila, and Gibson, John K. A Uranyl Peroxide Dimer in the Gas Phase. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.7b00187.
Dau, Phuong D., Dau, Phuong V., Rao, Linfeng, Kovacs, Attila, & Gibson, John K. A Uranyl Peroxide Dimer in the Gas Phase. United States. https://doi.org/10.1021/acs.inorgchem.7b00187
Dau, Phuong D., Dau, Phuong V., Rao, Linfeng, Kovacs, Attila, and Gibson, John K. Tue .
"A Uranyl Peroxide Dimer in the Gas Phase". United States. https://doi.org/10.1021/acs.inorgchem.7b00187. https://www.osti.gov/servlets/purl/1436151.
@article{osti_1436151,
title = {A Uranyl Peroxide Dimer in the Gas Phase},
author = {Dau, Phuong D. and Dau, Phuong V. and Rao, Linfeng and Kovacs, Attila and Gibson, John K.},
abstractNote = {For this study, the gas-phase uranyl peroxide dimer, [(UO2)2(O2)(L)2]2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO22+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO2)2(O)(L)2]2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO2)2(OH)2(L)2]2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide of particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO2)2(O2)(L)2]2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO2)2(O2)]2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.},
doi = {10.1021/acs.inorgchem.7b00187},
journal = {Inorganic Chemistry},
number = 7,
volume = 56,
place = {United States},
year = {Tue Mar 14 00:00:00 EDT 2017},
month = {Tue Mar 14 00:00:00 EDT 2017}
}
Web of Science
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