Computationally Guided Investigation of the Optical Spectra of Pure β-UO3

Tyler L. Spano; Ashley E. Shields; Brianna S. Barth; Jeremiah D. Gruidl; Jennifer L. Niedziela; Roger J. Kapsimalis; Andrew Miskowiec

doi:10.1021/acs.inorgchem.0c01279

Computationally Guided Investigation of the Optical Spectra of Pure β-UO₃

Tyler L. Spano, Ashley E. Shields, Brianna S. Barth, Jeremiah D. Gruidl, Jennifer L. Niedziela, Roger J. Kapsimalis, Andrew Miskowiec

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16 Scopus citations

Abstract

Single-phase β-UO3 is synthesized by flash heating UO2(NO3)·6H2O in air to 450 °C and annealing for 60 h under the same conditions. For the first time, we report the Raman spectra of pure β-UO3. To facilitate the assignment of Raman and infrared vibrational modes, we use density functional theory with density functional perturbation theory. By employing a novel analysis scheme that includes the mode frequencies as well as a quantitative analysis of the mode eigenvectors, we assign the observed spectral features to individual chemical modes. In particular, the density functional theory optimized structure, observed Raman spectrum, and eigenvector analysis suggest the presence of four crystallographically distinct uranyl ions, one more than has previously been suggested.

Original language	English
Pages (from-to)	11481-11492
Number of pages	12
Journal	Inorganic Chemistry
Volume	59
Issue number	16
DOIs	https://doi.org/10.1021/acs.inorgchem.0c01279
State	Published - Aug 17 2020

Funding

The authors thank Michael Lance for his assistance in collecting IR data, David Harris and Scott Matthews for their support, and Zach Brubaker and Sara Isbill for their helpful comments. We also thank two anonymous reviewers for their careful consideration of this work, which has been significantly improved by their comments. A portion of this research was conducted at the Center for Nanophase Materials Sciences, which is a Department of Energy Office of Science User Facility. This project was supported in part by an appointment to the Science Education Programs at National Institutes of Health, administered by Oak Ridge Associated Universities through the US Department of Energy Oak Ridge Institute for Science and Education. This research used resources of the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC05-00OR22725. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). 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 ).

Funders	Funder number
CADES
Data Environment for Science
US Department of Energy Oak Ridge Institute for Science and Education
National Institutes of Health
U.S. Department of Energy	DE-AC05-00OR22725
Office of Science
Oak Ridge Associated Universities

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10.1021/acs.inorgchem.0c01279

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title = "Computationally Guided Investigation of the Optical Spectra of Pure β-UO3",

abstract = "Single-phase β-UO3 is synthesized by flash heating UO2(NO3)·6H2O in air to 450 °C and annealing for 60 h under the same conditions. For the first time, we report the Raman spectra of pure β-UO3. To facilitate the assignment of Raman and infrared vibrational modes, we use density functional theory with density functional perturbation theory. By employing a novel analysis scheme that includes the mode frequencies as well as a quantitative analysis of the mode eigenvectors, we assign the observed spectral features to individual chemical modes. In particular, the density functional theory optimized structure, observed Raman spectrum, and eigenvector analysis suggest the presence of four crystallographically distinct uranyl ions, one more than has previously been suggested.",

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AU - Spano, Tyler L.

AU - Shields, Ashley E.

AU - Barth, Brianna S.

AU - Gruidl, Jeremiah D.

AU - Niedziela, Jennifer L.

AU - Kapsimalis, Roger J.

AU - Miskowiec, Andrew

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AB - Single-phase β-UO3 is synthesized by flash heating UO2(NO3)·6H2O in air to 450 °C and annealing for 60 h under the same conditions. For the first time, we report the Raman spectra of pure β-UO3. To facilitate the assignment of Raman and infrared vibrational modes, we use density functional theory with density functional perturbation theory. By employing a novel analysis scheme that includes the mode frequencies as well as a quantitative analysis of the mode eigenvectors, we assign the observed spectral features to individual chemical modes. In particular, the density functional theory optimized structure, observed Raman spectrum, and eigenvector analysis suggest the presence of four crystallographically distinct uranyl ions, one more than has previously been suggested.

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Computationally Guided Investigation of the Optical Spectra of Pure β-UO₃

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