Computational insights into the lattice dynamics of Pu(IV) oxalates

Sara B. Isbill; Elodia Ciprian; Jonathan H. Christian; Amy Hixon; Bryan J. Foley; Eliel Villa-Aleman; Andrew J. Miskowiec

doi:10.1016/j.jnucmat.2022.154106

Computational insights into the lattice dynamics of Pu(IV) oxalates

Sara B. Isbill, Elodia Ciprian, Jonathan H. Christian, Amy Hixon, Bryan J. Foley, Eliel Villa-Aleman, Andrew J. Miskowiec

Materials & Chemistry Group

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Despite its use in PuO₂ production, the structure of anhydrous Pu(C₂O₄)₂ is still not completely understood. Recently, two candidate structures for Pu(C₂O₄)₂ were proposed via density functional theory (DFT), after which the first experimental optical vibrational spectra were reported. Here, we calculated the lattice dynamics of the candidate structures using DFT and found that the primary difference between them is the presence of a vibrational mode near 1380 cm⁻¹ in one structure. The frequency and optical activity of this mode agree well with the published experimental results, providing strong support for this calculated structure as that of anhydrous Pu(C₂O₄)₂.

Original language	English
Article number	154106
Journal	Journal of Nuclear Materials
Volume	573
DOIs	https://doi.org/10.1016/j.jnucmat.2022.154106
State	Published - Jan 2023

Funding

This research used resources of CADES at ORNL, which is supported by the US Department of Energy's Office of Science under contract no. DE-AC05-00OR22725. Part of this work has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). Part of this work was produced by Battelle Savannah River Alliance, LLC under Contract No. 89303321CEM000080 and/or a predecessor contract with the U.S. Department of Energy. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). The authors would like to thank Dr. Ashley E. Shields and Dr. Erik Nykwest for helpful discussions. This research used resources of CADES at ORNL, which is supported by the US Department of Energy's Office of Science under contract no. DE-AC05-00OR22725 . Part of this work has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). Part of this work was produced by Battelle Savannah River Alliance, LLC under Contract No. 89303321CEM000080 and/or a predecessor contract with the U.S. Department of Energy. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). The authors would like to thank Dr. Ashley E. Shields and Dr. Erik Nykwest for helpful discussions.

Keywords

Density functional theory
Oxalates
Phonons
Plutonium
Raman

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title = "Computational insights into the lattice dynamics of Pu(IV) oxalates",

abstract = "Despite its use in PuO2 production, the structure of anhydrous Pu(C2O4)2 is still not completely understood. Recently, two candidate structures for Pu(C2O4)2 were proposed via density functional theory (DFT), after which the first experimental optical vibrational spectra were reported. Here, we calculated the lattice dynamics of the candidate structures using DFT and found that the primary difference between them is the presence of a vibrational mode near 1380 cm−1 in one structure. The frequency and optical activity of this mode agree well with the published experimental results, providing strong support for this calculated structure as that of anhydrous Pu(C2O4)2.",

keywords = "Density functional theory, Oxalates, Phonons, Plutonium, Raman",

author = "Isbill, {Sara B.} and Elodia Ciprian and Christian, {Jonathan H.} and Amy Hixon and Foley, {Bryan J.} and Eliel Villa-Aleman and Miskowiec, {Andrew J.}",

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doi = "10.1016/j.jnucmat.2022.154106",

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T1 - Computational insights into the lattice dynamics of Pu(IV) oxalates

AU - Isbill, Sara B.

AU - Ciprian, Elodia

AU - Christian, Jonathan H.

AU - Hixon, Amy

AU - Foley, Bryan J.

AU - Villa-Aleman, Eliel

AU - Miskowiec, Andrew J.

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N2 - Despite its use in PuO2 production, the structure of anhydrous Pu(C2O4)2 is still not completely understood. Recently, two candidate structures for Pu(C2O4)2 were proposed via density functional theory (DFT), after which the first experimental optical vibrational spectra were reported. Here, we calculated the lattice dynamics of the candidate structures using DFT and found that the primary difference between them is the presence of a vibrational mode near 1380 cm−1 in one structure. The frequency and optical activity of this mode agree well with the published experimental results, providing strong support for this calculated structure as that of anhydrous Pu(C2O4)2.

AB - Despite its use in PuO2 production, the structure of anhydrous Pu(C2O4)2 is still not completely understood. Recently, two candidate structures for Pu(C2O4)2 were proposed via density functional theory (DFT), after which the first experimental optical vibrational spectra were reported. Here, we calculated the lattice dynamics of the candidate structures using DFT and found that the primary difference between them is the presence of a vibrational mode near 1380 cm−1 in one structure. The frequency and optical activity of this mode agree well with the published experimental results, providing strong support for this calculated structure as that of anhydrous Pu(C2O4)2.

KW - Density functional theory

KW - Oxalates

KW - Phonons

KW - Plutonium

KW - Raman

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Computational insights into the lattice dynamics of Pu(IV) oxalates

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