Computational insights into the structure of anhydrous Pu(III) oxalate

Isbill, Sara B.; Miskowiec, Andrew J.

doi:10.1016/j.jnucmat.2024.155583

Computational insights into the structure of anhydrous Pu(III) oxalate

Journal Article · Fri Dec 20 00:00:00 EST 2024 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2024.155583· OSTI ID:2491455

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Despite the plutonium oxalate method's wide use in plutonium reprocessing, the method's mechanistic details remain unclear, particularly the identity of the plutonium oxidation state during conversion from an oxalate hydrate to the oxide. Recently, the optical vibrational spectra of Pu(III) oxalate during calcination were measured, providing an experimental reference for computational studies aimed at elucidating the oxalate structure. Here, in this work, we compare the vibrational and electronic properties of two candidate anhydrous Pu(III) oxalate structures calculated using density functional theory with recent experiments. We find that both structures are plausible and may coexist at experimental temperatures, providing insights into the broad features measured in the Raman and infrared spectra.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2491455

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 605; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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