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Title: 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 » uranyl peroxide nanostructures.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. 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.
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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
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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.
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@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}
}
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