Ab initio molecular dynamics (AIMD) simulations of NaCl, UCl3 molten salts

Andersson, Anders David Ragnar; Beeler, Ben W.

doi:10.1016/j.jnucmat.2022.153836

Ab initio molecular dynamics (AIMD) simulations of NaCl, UCl₃ molten salts

Journal Article · Thu Sep 01 00:00:00 EDT 2022 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2022.153836· OSTI ID:1872360

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Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
North Carolina State Univ., Raleigh, NC (United States); Idaho National Lab. (INL), Idaho Falls, ID (United States)

Ab initio molecular dynamics (AIMD) simulations are used to calculate select thermophysical and thermodynamic properties of NaCl, UCl and NaCl-UCl₃ molten salts. Following established approaches, the AIMD simulations include a model for Van der Waals interactions. The Langreth & Lundqvist (vDW-DF2), DFT-D3, and density-dependent energy correction (DFT-dDsC) dispersion models are first tested for molten NaCl in order to assess their accuracy for density and heat capacity predictions across a range of temperatures. Based on the NaCl results, the vdW-DF2 and DFT-dDsC methods are extended to the UCl₃ system and compared to available experimental data. Next, mixtures of NaCl-UCl₃ are investigated and analyzed with respect to the deviation from ideal solution behavior. For the DFT-dDsC simulations, density deviates by up to 2% from an ideal mixture, with the maximum occurring close to the eutectic composition. The mixing energy also deviates from an ideal solution and exhibits a minimum of about -0.074 to eV per formula unit, again close to the eutectic composition. Finally, the compressibility and species diffusivity of the pure and mixed salt systems are calculated. The diffusivities are slightly reduced in the mixed compared to the pure systems and the compressibilities loosely follow a linear correlation as a function of the UCl₃ composition. The trends observed for mixing properties are rationalized by correlating them to the coordination chemistry, which emphasizes the importance of maintaining the extended network formed by U and Cl ions as the NaCl concentration increases. The concentration at which breakdown of the extended network occurs, roughly coincides with the minimum of both the mixing energy and the deviation from ideal solution behavior for density.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Nuclear Energy (NE), Nuclear Energy Advanced Modeling and Simulation (NEAMS)

Grant/Contract Number:: 89233218CNA000001; AC07-05ID14517

OSTI ID:: 1872360

Alternate ID(s):: OSTI ID: 1903273

Report Number(s):: INL/JOU-22-68109-Rev000; LA-UR-22-20387

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 568; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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