Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water

Harindu Rajapaksha; Samantha J Kruse; Jay A. LaVerne; Sara E Mason; Tori Z Forbes

doi:10.1021/acs.inorgchem.5c00693

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Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water

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Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water

Harindu Rajapaksha, Samantha J Kruse, Jay A. LaVerne, Sara E Mason and Tori Z Forbes

Inorganic chemistry, Vol.64(19), pp.9652-9661

05/19/2025

DOI: 10.1021/acs.inorgchem.5c00693

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Abstract

Nuclear materials, such as uranium-bearing solids, are exposed to high levels of ionizing radiation throughout the nuclear fuel cycle; thus, it is important to develop a molecular-level understanding of how these materials behave and degrade in the presence of gamma (γ) irradiation. In the current study, three U(VI) tetrachloride complexes, M2[UO2Cl4]·xH2O (where M = K+, Rb+, or Cs+ and x = 0 or 2), and their respective chloride salts were exposed to 1–50 kGy of γ radiation using a 60Co source. Irradiated materials were evaluated by using electron paramagnetic resonance (EPR) and Raman spectroscopy and were further explored by using density functional theory (DFT) methods. EPR spectra of the irradiated materials suggest the formation of a Cl-based radical for both the alkali salts and the uranyl tetrachloride compounds, and DFT calculations provide evidence that the Cl2–• radical is formed within these materials. The presence of water in the K+ and Rb+ compounds leads to additional spectroscopic signatures that could be traced back to water radiolysis and the formation of peroxide and superoxide species. DFT results support the formation of HO2• in the lattice and potentially the formation of a [UO2Cl3(O2)]3– species, highlighting the impact of water within the hydrated material to alter U(VI) speciation by radiolysis.

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Details

Title: Subtitle: Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water
Creators: Harindu Rajapaksha - University of Iowa
Samantha J Kruse - University of Iowa
Jay A. LaVerne - University of Notre Dame
Sara E Mason - University of Iowa, Chemistry
Tori Z Forbes - University of Iowa, Chemistry
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.64(19), pp.9652-9661
DOI: 10.1021/acs.inorgchem.5c00693
ISSN: 0020-1669
eISSN: 1520-510X
Publisher: American Chemical Society
Language: English
Electronic publication date: 05/07/2025
Date published: 05/19/2025
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984817174402771

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