Computational study of HCl adsorption on stoichiometric and oxygen vacancy PuO2 {111}, {110} and {100} surfaces

Collard, Jonathan; Steele, Helen; Kaltsoyannis, Nikolas

doi:10.1016/j.jnucmat.2019.151951

Cited by 12 publications

(3 citation statements)

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“…Molecular thermodynamics was employed to calculate the relationship between the water desorption temperature and the partial pressure of water. The method used was as described in our recently published paper . This is similar to the approach used to calculate the water desorption temperature from AnO 2 (An = U, Pu) surfaces in our previous work, which was itself based on Molinari et al’s work on water desorption from ceria surfaces .…”

Section: Computational Detailsmentioning

confidence: 99%

“…Previous theoretical work in this area mainly focuses on the study of pure PuO 2 and AmO 2 , ,,,,− although CeO 2 has also been well studied. − Not only is CeO 2 interesting in its own right and possesses the same fluorite structure as PuO 2 , but it is often used experimentally as a nonradioactive surrogate for PuO 2 , and computational evaluations of that similarity are useful. However, there are very few theoretical studies of Pu-Am MOX.…”

Section: Introductionmentioning

confidence: 99%

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Computational Study of Plutonium–Americium Mixed Oxides (Pu_0.92Am_0.08O_2–x); Water Adsorption on {111}, {110}, and {100} Surfaces

Chen

Kaltsoyannis

2020

J. Phys. Chem. C

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Hubbard U-corrected generalized gradient approximation density functional theory is used to study the surface properties of plutonium−americium mixed dioxides (Pu-Am MOX). Stoichiometric and oxygen vacancy defect {111}, {110}, and {100} surfaces are investigated, including the molecular and dissociative adsorptions of water. Comparison with previous work from our group on PuO 2 and AmO 2 leads to the conclusion that substituted Am gains electrons from the PuO 2 slab. In agreement with previous experimental studies, when the oxygen to metal ratio of MOX decreases, substituted Am is reduced to the trivalent state before the reduction of Pu. The geometries of water adsorption are similar to adsorption on PuO 2 and AmO 2 surfaces, while the presence of Am in PuO 2 surfaces promotes water adsorption. Higher temperature is required for dissociation of molecularly adsorbed water on Pu-Am MOX than on the corresponding PuO 2 surfaces, while desorption of dissociatively adsorbed water on PuO 2 is harder than on the corresponding MOX surfaces.

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Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Computational Study of Plutonium–Americium Mixed Oxides (Pu_0.92Am_0.08O_2–x); Water Adsorption on {111}, {110}, and {100} Surfaces

Chen

Kaltsoyannis

2020

J. Phys. Chem. C

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“…Indeed, standard DFT functionals can yield erroneous predictions for actinide materials, most notably the failure of GGA functionals to reproduce the experimentally determined insulating behavior of the actinide dioxides; the over-delocalization of the 5f electrons by the GGA approach incorrectly predicts these oxides to be metallic . This is typically corrected by the application of the Hubbard U term, which reduces the 5f delocalization. − …”

Section: Introductionmentioning

confidence: 99%

Incorporation of Kr and Xe in Uranium Mononitride: A Density Functional Theory Study

Lin

Kaltsoyannis

2021

J. Phys. Chem. C

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Uranium nitride is a material of considerable fundamental interest and is a promising candidate for an advanced nuclear fuel. We here study intrinsic point defects and incorporation of the fission gas atoms Kr and Xe in UN by density functional theory, including the first report of the effects of nonstoichiometry. The defect formation energies of U and N vacancies are found to be highly dependent on stoichiometry. The most stable defect types are N vacancies under U-rich and near-stoichiometric conditions but U vacancies under N-rich conditions. The existence of a defect significantly affects the magnetic moment of UN, especially defects involving U vacancies. The incorporation of Kr and Xe in UN induces relaxation of the atomic positions of U and N atoms adjacent to Kr or Xe, with the displacement induced by Xe being more significant than that by Kr due to the larger atomic radius of the former. The calculated solution energy of Kr and Xe in a perfect UN supercell shows that the most energetically favorable sites are Schottky defects and U vacancies under U-rich and N-rich conditions, respectively. Under near-stoichiometric conditions, Kr and Xe behave differently, with the former preferring a U vacancy and the latter preferring the Schottky defect. Bader charge analysis indicates larger charge transfer to noble gases on Kr incorporation than on Xe incorporation, consistent with the higher electronegativity of Kr.

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The adsorption thermodynamics of H2O and CO2 on PuO2(1 1 1) surface: A comparative study based on DFT+U-D3

Zhang

Sun

Zhang

et al. 2021

Applied Surface Science

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Computational study of HCl adsorption on stoichiometric and oxygen vacancy PuO2 {111}, {110} and {100} surfaces

Cited by 12 publications

References 51 publications

Computational Study of Plutonium–Americium Mixed Oxides (Pu_0.92Am_0.08O_2–x); Water Adsorption on {111}, {110}, and {100} Surfaces

Computational Study of Plutonium–Americium Mixed Oxides (Pu_0.92Am_0.08O_2–x); Water Adsorption on {111}, {110}, and {100} Surfaces

Incorporation of Kr and Xe in Uranium Mononitride: A Density Functional Theory Study

The adsorption thermodynamics of H2O and CO2 on PuO2(1 1 1) surface: A comparative study based on DFT+U-D3

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Computational study of HCl adsorption on stoichiometric and oxygen vacancy PuO2 {111}, {110} and {100} surfaces

Cited by 12 publications

References 51 publications

Computational Study of Plutonium–Americium Mixed Oxides (Pu0.92Am0.08O2–x); Water Adsorption on {111}, {110}, and {100} Surfaces

Computational Study of Plutonium–Americium Mixed Oxides (Pu0.92Am0.08O2–x); Water Adsorption on {111}, {110}, and {100} Surfaces

Incorporation of Kr and Xe in Uranium Mononitride: A Density Functional Theory Study

The adsorption thermodynamics of H2O and CO2 on PuO2(1 1 1) surface: A comparative study based on DFT+U-D3

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Product

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Computational Study of Plutonium–Americium Mixed Oxides (Pu_0.92Am_0.08O_2–x); Water Adsorption on {111}, {110}, and {100} Surfaces

Computational Study of Plutonium–Americium Mixed Oxides (Pu_0.92Am_0.08O_2–x); Water Adsorption on {111}, {110}, and {100} Surfaces