Polymorphism and phase transitions in layered uranium(VI) hydroxides: Ab initio lattice dynamics simulations of UO2(OH)2

Weck, Philippe F.; Kim, Eunja

doi:10.1063/5.0242688

Title: Polymorphism and phase transitions in layered uranium(VI) hydroxides: Ab initio lattice dynamics simulations of UO₂(OH)₂

Journal Article · 11 December 2024 · Journal of Applied Physics

DOI: https://doi.org/10.1063/5.0242688 · OSTI ID:2481178

^[1];

^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of Texas at El Paso, TX (United States)

The phase transitions and thermodynamics of stoichiometric α-, β-, and γ-UO₂(OH)₂ polymorphs are investigated using density functional perturbation theory. The pressure-induced β(Pbca) → α(Cmca) phase transition is reproduced by calculations, with a volume reduction of ΔV/V = -14.7% similar to experiment. Consistent with observation, a temperature-driven γ(P2₁/c) → β(Pbca) phase transition is predicted near 533 K. At 298.15K, the computed standard molar heat capacity of α-UO₂(OH)₂ is C_p⁰ = 112.1 J mol^-1 K^-1, only 1.6% smaller than the value of C_p⁰ = 113.96 ± 0.12 J mol^-1 K^-1 measured by calorimetry. C_p⁰ = 112.4 and 104.8 J mol^-1 K^-1 are predicted for the β- and γ-UO₂(OH)₂ polymorphs, respectively. The calculated molar enthalpy and Gibbs energy functions of the α-, β-, and γ-UO₂(OH)₂ polymorphs are also reported.

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Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Office of Spent Fuel and Waste Disposition; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 2481178

Report Number(s):: SAND--2024-16673J

Journal Information:: Journal of Applied Physics, Journal Name: Journal of Applied Physics Journal Issue: 22 Vol. 136; ISSN 0021-8979

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Polymorphism and phase transitions in layered uranium(VI) hydroxides: Ab initio lattice dynamics simulations of UO2(OH)2

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Title: Polymorphism and phase transitions in layered uranium(VI) hydroxides: Ab initio lattice dynamics simulations of UO₂(OH)₂