Insights into the thermal decomposition of plutonium(IV) oxalate – a DFT study of the intermediate structures

South, Christopher J.; Roy, Lindsay E.

doi:10.1016/j.jnucmat.2021.152864

Insights into the thermal decomposition of plutonium(IV) oxalate – a DFT study of the intermediate structures

Journal Article · Sun Feb 07 00:00:00 EST 2021 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2021.152864· OSTI ID:1805215

South, Christopher J. ^[1]; Roy, Lindsay E. ^[1]

Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

The thermal decomposition of plutonium oxalate to oxide is one of the most studied reactions in actinide chemistry but the intermediates have been the subject of debate for decades. Recent experimental data suggest that the decomposition of Pu(IV) oxalate in air undergoes dehydration first, then reduction to Pu(III) oxalate. The precise structural modifications that take place are unknown as experiments have not been able to fully characterize the intermediates at the microscopic level. To rectify this, we employed solid state density functional theory calculations at the PBE-D3 level with a Hubbard U correction to model the structures and energetics of potential dehydrated Pu(IV) and Pu(III) oxalate intermediate compounds. Based on the theoretical study presented here, the anhydrous analogues of the known hydrated Pu(IV) and Pu(III) oxalates are the preferred crystal structures formed through an overall exothermic reaction process. However, decomposition could proceed through the formation of a higher energy, more complicated 3D lattice structure with frustrated oxalate binding. It is expected that the intermediates presented here could be identified using spectroscopic techniques to enable further insight into the reaction mechanism.

View Accepted Manuscript (DOE)

Research Organization:: Savannah River National Lab (SRNL), Aiken, SC (United States); Savannah River Site (SRS), Aiken, SC (United States)

Sponsoring Organization:: USDOE Office of Environmental Management (EM)

Grant/Contract Number:: AC09-08SR22470

OSTI ID:: 1805215

Report Number(s):: SRNL--STI-2021-00079

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 549; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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