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The defect chemistry of non-stoichiometric PuO2±x

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The defect chemistry of non-stoichiometric PuO2±x. / Neilson, W.D.; Pegg, J.T.; Steele, H. et al.
In: Physical Chemistry Chemical Physics, Vol. 23, No. 8, 11.02.2021, p. 4544-4554.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Neilson, WD, Pegg, JT, Steele, H & Murphy, ST 2021, 'The defect chemistry of non-stoichiometric PuO2±x', Physical Chemistry Chemical Physics, vol. 23, no. 8, pp. 4544-4554. https://doi.org/10.1039/d0cp06497a

APA

Neilson, W. D., Pegg, J. T., Steele, H., & Murphy, S. T. (2021). The defect chemistry of non-stoichiometric PuO2±x. Physical Chemistry Chemical Physics, 23(8), 4544-4554. https://doi.org/10.1039/d0cp06497a

Vancouver

Neilson WD, Pegg JT, Steele H, Murphy ST. The defect chemistry of non-stoichiometric PuO2±x. Physical Chemistry Chemical Physics. 2021 Feb 11;23(8):4544-4554. doi: 10.1039/d0cp06497a

Author

Neilson, W.D. ; Pegg, J.T. ; Steele, H. et al. / The defect chemistry of non-stoichiometric PuO2±x. In: Physical Chemistry Chemical Physics. 2021 ; Vol. 23, No. 8. pp. 4544-4554.

Bibtex

@article{763e75e7ce44468fb2541d9c93794c62,
title = "The defect chemistry of non-stoichiometric PuO2±x",
abstract = "An increased knowledge of the chemistry of PuO2is imperative for the design of procedures to store, dispose, or make use of PuO2. In this work, point defect concentrations in PuO2are determined by combining density functional theory (DFT) defect energies and empirical potential calculations of vibrational entropies. The obtained defect concentrations are expressed as a function of temperature and oxygen partial pressure and used to calculate non-stoichiometry in PuO2±x. The results show that the defect chemistry of PuO2is dominated by oxygen vacancies and interstitials. Hypo-stoichiometric PuO2−xis accommodated by both the uncharged oxygen vacancy and positively charged oxygen vacancy at small values ofx, withincreasingly dominant with increasingx. The negatively charged oxygen interstitial (O2−i) is found to accommodate hyper-stoichiometry (PuO2+x), but reluctance to form hyper-stoichiometric PuO2+xis observed, with oxygen interstitials present only in very low concentrations irrespective of conditions. The small degree of hyper-stoichiometry found is favoured by low temperatures. {\textcopyright} the Owner Societies 2021.",
keywords = "Density functional theory, Design for testability, Stoichiometry, Defect concentrations, Empirical potentials, Low concentrations, Non-stoichiometric, Oxygen interstitials, Oxygen partial pressure, Positively charged, Vibrational entropy, Oxygen vacancies",
author = "W.D. Neilson and J.T. Pegg and H. Steele and S.T. Murphy",
year = "2021",
month = feb,
day = "11",
doi = "10.1039/d0cp06497a",
language = "English",
volume = "23",
pages = "4544--4554",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "8",

}

RIS

TY - JOUR

T1 - The defect chemistry of non-stoichiometric PuO2±x

AU - Neilson, W.D.

AU - Pegg, J.T.

AU - Steele, H.

AU - Murphy, S.T.

PY - 2021/2/11

Y1 - 2021/2/11

N2 - An increased knowledge of the chemistry of PuO2is imperative for the design of procedures to store, dispose, or make use of PuO2. In this work, point defect concentrations in PuO2are determined by combining density functional theory (DFT) defect energies and empirical potential calculations of vibrational entropies. The obtained defect concentrations are expressed as a function of temperature and oxygen partial pressure and used to calculate non-stoichiometry in PuO2±x. The results show that the defect chemistry of PuO2is dominated by oxygen vacancies and interstitials. Hypo-stoichiometric PuO2−xis accommodated by both the uncharged oxygen vacancy and positively charged oxygen vacancy at small values ofx, withincreasingly dominant with increasingx. The negatively charged oxygen interstitial (O2−i) is found to accommodate hyper-stoichiometry (PuO2+x), but reluctance to form hyper-stoichiometric PuO2+xis observed, with oxygen interstitials present only in very low concentrations irrespective of conditions. The small degree of hyper-stoichiometry found is favoured by low temperatures. © the Owner Societies 2021.

AB - An increased knowledge of the chemistry of PuO2is imperative for the design of procedures to store, dispose, or make use of PuO2. In this work, point defect concentrations in PuO2are determined by combining density functional theory (DFT) defect energies and empirical potential calculations of vibrational entropies. The obtained defect concentrations are expressed as a function of temperature and oxygen partial pressure and used to calculate non-stoichiometry in PuO2±x. The results show that the defect chemistry of PuO2is dominated by oxygen vacancies and interstitials. Hypo-stoichiometric PuO2−xis accommodated by both the uncharged oxygen vacancy and positively charged oxygen vacancy at small values ofx, withincreasingly dominant with increasingx. The negatively charged oxygen interstitial (O2−i) is found to accommodate hyper-stoichiometry (PuO2+x), but reluctance to form hyper-stoichiometric PuO2+xis observed, with oxygen interstitials present only in very low concentrations irrespective of conditions. The small degree of hyper-stoichiometry found is favoured by low temperatures. © the Owner Societies 2021.

KW - Density functional theory

KW - Design for testability

KW - Stoichiometry

KW - Defect concentrations

KW - Empirical potentials

KW - Low concentrations

KW - Non-stoichiometric

KW - Oxygen interstitials

KW - Oxygen partial pressure

KW - Positively charged

KW - Vibrational entropy

KW - Oxygen vacancies

U2 - 10.1039/d0cp06497a

DO - 10.1039/d0cp06497a

M3 - Journal article

VL - 23

SP - 4544

EP - 4554

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 8

ER -