A Uranyl Peroxide Dimer in the Gas Phase

Dau, Phuong D.; Dau, Phuong V.; Rao, Linfeng; Kovacs, Attila; Gibson, John K.

doi:10.1021/acs.inorgchem.7b00187

Title: A Uranyl Peroxide Dimer in the Gas Phase

Journal Article · Tue Mar 14 00:00:00 EDT 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b00187· OSTI ID:1436151

Dau, Phuong D. ^[1]; Dau, Phuong V. ^[1]; Rao, Linfeng ^[1];

^[2];

^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
European Commission, Karlsruhe (Germany). Joint Research Centre

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.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1436151

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 7; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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