Radiation‐Induced Defects in Uranyl Trinitrate Solids

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

doi:10.1002/chem.202400956

Title: Radiation‐Induced Defects in Uranyl Trinitrate Solids

Journal Article · Fri May 31 00:00:00 UTC 2024 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202400956 · OSTI ID:2369011

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^[1]; LaVerne, Jay A. ^[2]; Mason, Sara E. ^[3];

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Department of Chemistry University of Iowa University of Iowa Chemistry Building Iowa City IA USA 52242
Radiation Laboratory University of Notre Dame Notre Dame IN USA 46556, Department of Physics and Astronomy University of Notre Dame Notre Dame IN USA 46556
Department of Chemistry University of Iowa University of Iowa Chemistry Building Iowa City IA USA 52242, Center for Functional Nanomaterials Brookhaven National Laboratory Upton NY USA 11973

Abstract Actinides are inherently radioactive; thus, ionizing radiation is emitted by these elements can have profound effects on its surrounding chemical environment through the formation of free radical species. While previous work has noted that the presence of free radicals in the system impacts the redox state of the actinides, there is little atomistic understanding of how these metal cations interact with free radicals. Herein, we explore the effects of radiation (UV and γ) on three U(VI) trinitrate complexes, M[UO ₂ (NO ₃ ) ₃ ] (where M=K ⁺ , Rb ⁺ , Cs ⁺ ), and their respective nitrate salts in the solid state via electron paramagnetic resonance (EPR) and Raman spectroscopy paired with Density Functional Theory (DFT) methods. We find that the alkali salts form nitrate radicals under UV and γ irradiation, but also note the presence of additional degradation products. M[UO ₂ (NO ₃ ) ₃ ] solids also form nitrate radicals and additional DFT calculations indicate the species corresponds to a change from the bidentate bound nitrate anion into a monodentate NO ₃ ^• radical. Computational studies also highlight the need to include the second sphere coordination environment around the [UO ₂ (NO ₃ ) ₃ ] ^0,1 species to gain agreement between the experimental and predicted EPR signatures.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Notre Dame Radiation Laboratory (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: FC02-04ER15533; SC0012704; SC0021420

OSTI ID:: 2369011

Report Number(s):: BNL--225566-2024-JAAM; e202400956

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 35 Vol. 30; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
EPR
Raman
actinides
characterization
computational
defects
radiation
radicals
vibrational analysis

Title: Radiation‐Induced Defects in Uranyl Trinitrate Solids

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