Structural, thermodynamic, and electronic properties of plutonium oxides from first principles

Jomard, Gérald; Amadon, Bernard; Bottin, François; Torrent, Marc

doi:10.1103/physrevb.78.075125

Cited by 238 publications

(236 citation statements)

References 72 publications

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“…Since the GGA+U and LDA+U give the similar description of the PDOS, here we only plot the GGA+U results. The orbital-resolved PDOS of the bulk PuO 2 at the ground state has been calculated and analyzed in detail by previous DFT+U [19,21,22,24] and hybrid DFT [9,16] studies, and those theoretical results of DOS are usually tested by comparing with the experimental photoelectron spectroscopy (PES) measurements [6,7].…”

Section: Resultsmentioning

confidence: 99%

“…The exchange and correlation effects are treated in both the LDA and the GGA [31], based on which the strong on-site Coulomb repulsion among the localized Pu 5f electrons is described by using the LDA/GGA+U formalisms formulated by Dudarev et al [13][14][15]. As concluded in some previous DFT studies [19,20,22,24], although the pure LDA and GGA fail to depict the electronic structure, especially the insulating nature and the occupied-state character of bulk AFM PuO 2 , the LDA/GGA+U approaches can capture the Mott insulating properties of the strongly correlated Pu 5f electrons adequately and well reproduce experimental ground-state parameters by tuning the effective Hubbard parameter U eff at ∼4 eV.…”

Section: A Dft Calculationsmentioning

confidence: 99%

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First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

Sun

Liu

Song

et al. 2012

Journal of Nuclear Materials

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The (111), (110), and (001) surfaces properties of PuO 2 are studied by using density-functional theory+U method. The total-energy static calculations determine the relative order of stability for low-index PuO 2 surfaces, namely, O-terminated (111) > (110) > defective (001) > polar (001).The effect of thickness is shown to modestly modulate the surface stability and chemical activity of the (110) (111) is found to be the most stable surface. Whereas under O-reducing conditions, the on-surface O-vacancy of C V = 1/9 is stable, and for high reducing conditions, the (111) surface with nearly one monolayer subsurface oxygen removed (C V = 8/9) becomes most stable.

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Section: Resultsmentioning

confidence: 99%

Section: A Dft Calculationsmentioning

confidence: 99%

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

Sun

Liu

Song

et al. 2012

Journal of Nuclear Materials

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“…However, it is known that this method may introduce metastable states 18 with no physical meaning. This issue was extensively investigated for the UN system by Claisse et al 19 , where the occupation matrix control (OMC) scheme was used to avoid metastable states in this material 20 . Using the combination of DFT+U+OMC, the equilibrium properties of C and O in UN bulk were computed by Lopes et al 21 .…”

Section: Introductionmentioning

confidence: 99%

Transport properties of C and O in UN fuels

et al. 2017

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Uranium nitride fuel is considered for fast reactors (GEN-IV generation and space reactors) and for light water reactors as a high-density fuel option. Despite this large interest, there is a lack of information about its behavior for in-pile and out-of-pile conditions. From the present literature, it is known that C and O impurities have significant influence on the fuel performance. Here, we perform a systematic study of these impurities in the UN matrix using electronic-structure calculations of solute-defect interactions and microscopic jump frequencies. These quantities were calculated in the DFT+U approximation combined with the occupation matrix control scheme, to avoid convergence to metastable states for the 5f levels. The transport coefficients of the system were evaluated with the self-consistent mean-field theory. It is demonstrated that carbon and oxygen impurities have different diffusion properties in the UN matrix, with O atoms having a higher mobility, and C atoms showing a strong flux coupling anisotropy. The kinetic interplay between solutes and vacancies is expected to be the main cause for surface segregation, as incorporation energies show no strong thermodynamic segregation preference for (001)-surfaces compared with the bulk.

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“…The effective modification of pure DFT by LDA/GGA+U formalisms has been confirmed widely in studies of PuO 2 [27][28][29][30][31][32][33][34][35], which have reported the AFM-insulator ground state of…”

Section: Introductionmentioning

confidence: 98%

The environmental dependence of redox energetics of PuO2 and α-Pu2O3: A quantitative solution from

et al. 2012

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We report a comprehensive density functional theory (DFT) + U study of the energetics of charged and neutral oxygen defects in both PuO 2 and α-Pu 2 O 3 , and present a quantitative determination of the equilibrium compositions of reduced PuO 2 (PuO 2−x ) as functions of environmental temperature and partial pressure of oxygen, which shows fairly agreement with corresponding high-temperature experiments. Under ambient conditions, the endothermic reduction of PuO 2 to α-Pu 2 O 3 is found to be facilitated by accompanying volume expansion of PuO 2−x and the possible migration of O-vacancy, whereas further reduction of α-Pu 2 O 3 is predicted to be much more difficult. In contrast to the endothermic oxidation of PuO 2 , the oxidation of α-Pu 2 O 3 is a stable exothermic process.

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Structural, thermodynamic, and electronic properties of plutonium oxides from first principles

Cited by 238 publications

References 72 publications

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

Transport properties of C and O in UN fuels

The environmental dependence of redox energetics of PuO2 and α-Pu2O3: A quantitative solution from

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