In Situ High-Temperature Raman Spectroscopy of UCl3: A Combined Experimental and Theoretical Study

Strzelecki, Andrew Charles; Wang, Gaoxue; Hickam, Sarah Margaret; Parker, Stephen Scott; Batrice, Rami John; Jackson, Jay Matt; Conroy, Nathan Alec; Mitchell, Jeremy Neil; Andersson, David A.; Monreal, Marisa Jennifer; Boukhalfa, Hakim; Xu, Hongwu

doi:10.1021/acs.inorgchem.3c03139

Title: In Situ High-Temperature Raman Spectroscopy of UCl₃: A Combined Experimental and Theoretical Study

Journal Article · 01 November 2023 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.3c03139 · OSTI ID:2205066

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Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Arizona State University, Tempe, AZ (United States)

Uranium trichloride (UCl₃) has received growing interest for its use in uranium-fueled molten salt reactors and in the pyrochemical processing of used fuel. In this paper, we report for the first time the experimentally determined Raman spectra of UCl₃, at both ambient condition and in situ high temperatures up to 871 K. The frequencies of five of the Raman-active vibrational modes (v_i) of UCl₃ exhibit a negative temperature derivative ((∂ν_i/∂T)_P) with increasing temperature. Here, this red-shift behavior is likely due to the elongation of U–Cl bonds. The average isobaric mode Grüneisen parameter (γ_iP = 0.91 ± 0.02) of UCl₃ was determined through use of the coefficient of thermal expansion published in Vogel et al. (2021) and the (∂_νi/∂T)_P values determined in this study. These results are in general agreement with those calculated here by density functional theory (DFT+U). Finally, a comparison of the ambient band positions of UCl₃ to those of isostructural lanthanide (La–Eu) and actinide chlorides (Am–Cf) has been made.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001; NE0009444

OSTI ID:: 2205066

Report Number(s):: LA-UR--23-30105

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 45 Vol. 62; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: In Situ High-Temperature Raman Spectroscopy of UCl3: A Combined Experimental and Theoretical Study

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Title: In Situ High-Temperature Raman Spectroscopy of UCl₃: A Combined Experimental and Theoretical Study