The corrosion and oxidation of actinide metals, leading to the formation of metal-oxide surface layers with the catalytic evolution of hydrogen, impacts the management of nuclear materials. Here, the interaction of hydrogen with actinide dioxide (AnO2, An = U, Np, or Pu) (011) surfaces by Hubbard corrected density functional theory (PBEsol+U) has been studied, including spin–orbit interactions and non-collinear 3k anti-ferromagnetic behavior. The actinide dioxides crystalize in the fluorite-type structure, and although the (111) surface dominates the crystal morphology, the (011) surface energetics may lead to more significant interaction with hydrogen. The dissociative adsorption of hydrogen on the UO2 (0.44 eV), NpO2 (−0.47 eV), and PuO2 (−1.71 eV) (011) surfaces has been calculated. It is found that hydrogen dissociates on the PuO2 (011) surface; however, UO2 (011) and NpO2 (011) surfaces are relatively inert. Recombination of hydrogen ions is likely to occur on the UO2 (011) and NpO2 (011) surfaces, whereas hydroxide formation is shown to occur on the PuO2 (011) surface, which distorts the surface structure.
REFERENCES
1.
H. E.
Sims
, K. J.
Webb
, J.
Brown
, D.
Morris
, and R. J.
Taylor
, “Hydrogen yields from water on the surface of plutonium dioxide
,” J. Nucl. Mater.
437
(1
), 359
–364
(2013
).2.
J.
Meesungnoen
and J.-P.
Jay-Gerin
, “Radiolysis of supercritical water at 400 °C: Density dependence of the rate constant for the reaction of hydronium ions with hydrated electrons
,” Phys. Chem. Chem. Phys.
21
, 9141
(2019
).3.
J. M.
Haschke
, “Corrosion of uranium in air and water vapor: Consequences for environmental dispersal
,” J. Alloys Compd.
278
(1–2
), 149
–160
(1998
).4.
J. M.
Haschke
, T. H.
Allen
, and L. A.
Morales
, “Surface and corrosion chemistry of plutonium
,” Los Alamos Sci.
26
, 252
(2000
).5.
J. M.
Haschke
, T. H.
Allen
, and J. L.
Stakebake
, “Reaction kinetics of plutonium with oxygen, water and humid air: Moisture enhancement of the corrosion rate
,” J. Alloys Compd.
243
(1–2
), 23
–35
(1996
).6.
J. M.
Haschke
and J. C.
Martz
, “Catalyzed corrosion of plutonium: Hazards and applications
,” Los Alamos Sci.
26
, 266
(2000
).7.
L.
Zhang
, B.
Sun
, Q.
Zhang
, H.
Liu
, K.
Liu
, and H.
Song
, “First-principles study of the hydrogen resistance mechanism of PuO2
,” ACS Omega
5
(13
), 7211
–7218
(2020
).8.
J. T.
Pegg
, X.
Aparicio-Anglès
, M.
Storr
, and N. H.
de Leeuw
, “DFT+U study of the structures and properties of the actinide dioxides
,” J. Nucl. Mater.
492
, 269
–278
(2017
).9.
J. T.
Pegg
, A. E.
Shields
, M. T.
Storr
, D. O.
Scanlon
, and N. H.
de Leeuw
, “Noncollinear relativistic DFT + U calculations of actinide dioxide surfaces
,” J. Phys. Chem. C
123
(1
), 356
–366
(2019
).10.
J. T.
Pegg
, A. E.
Shields
, M. T.
Storr
, A. S.
Wills
, D. O.
Scanlon
, and N. H.
de Leeuw
, “Hidden magnetic order in plutonium dioxide nuclear fuel
,” Phys. Chem. Chem. Phys.
20
(32
), 20943
–20951
(2018
).11.
J. T.
Pegg
, A. E.
Shields
, M. T.
Storr
, A. S.
Wills
, D. O.
Scanlon
, and N. H.
de Leeuw
, “Magnetic structure of UO2 and NpO2 by first-principle methods
,” Phys. Chem. Chem. Phys.
21
(2
), 760
–771
(2019
).12.
A. E.
Shields
, A Computational Analysis of Thorium Dioxide and Th(1−x) UxO2 Systems
(UCL-University College London
, 2015
).13.
A. E.
Shields
, D.
Santos-Carballal
, and N. H.
de Leeuw
, “A density functional theory study of uranium-doped thoria and uranium adatoms on the major surfaces of thorium dioxide
,” J. Nucl. Mater.
473
, 99
–111
(2016
).14.
A. E.
Shields
, A. J.
Miskowiec
, J. L.
Niedziela
, M. C.
Kirkegaard
, K.
Maheshwari
, M. W.
Ambrogio
, R. J.
Kapsimalis
, and B. B.
Anderson
, “Shining a light on amorphous U2O7: A computational approach to understanding amorphous uranium materials
,” Opt. Mater.
89
, 295
–298
(2019
).15.
B.
Ao
and R.
Qiu
, “First-principles explorations of the universal picture of oxide layer structure over metallic plutonium
,” Corros. Sci.
153
, 236
(2019
).16.
J. P.
Perdew
and A.
Zunger
, “Self-interaction correction to density-functional approximations for many-electron systems
,” Phys. Rev. B
23
(10
), 5048
–5079
(1981
).17.
P.
Hohenberg
and W.
Kohn
, “Inhomogeneous electron gas
,” Phys. Rev.
136
(3B
), B864
–B871
(1964
).18.
W.
Kohn
and L. J.
Sham
, “Self-consistent equations including exchange and correlation effects
,” Phys. Rev.
140
(4A
), A1133
–A1138
(1965
).19.
S. L.
Dudarev
, G. A.
Botton
, S. Y.
Savrasov
, C. J.
Humphreys
, and A. P.
Sutton
, “Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
,” Phys. Rev. B
57
(3
), 1505
–1509
(1998
).20.
A. I.
Liechtenstein
, V. I.
Anisimov
, and J.
Zaanen
, “Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
,” Phys. Rev. B
52
(8
), R5467
–R5470
(1995
).21.
V. I.
Anisimov
, J.
Zaanen
, and O. K.
Andersen
, “Band theory and Mott insulators: Hubbard U instead of Stoner I
,” Phys. Rev. B
44
(3
), 943
–954
(1991
).22.
C.
Adamo
and V.
Barone
, “Toward reliable density functional methods without adjustable parameters: The PBE0 model
,” J. Chem. Phys.
110
(13
), 6158
–6170
(1999
).23.
J.
Heyd
, G. E.
Scuseria
, and M.
Ernzerhof
, “Hybrid functionals based on a screened Coulomb potential
,” J. Chem. Phys.
118
(18
), 8207
–8215
(2003
).24.
I. D.
Prodan
, G. E.
Scuseria
, and R. L.
Martin
, “Covalency in the actinide dioxides: Systematic study of the electronic properties using screened hybrid density functional theory
,” Phys. Rev. B
76
(3
), 033101
(2007
).25.
M. E.
Hoover
, R.
Atta-Fynn
, and A. K.
Ray
, “Surface properties of uranium dioxide from first principles
,” J. Nucl. Mater.
452
(1
), 479
–485
(2014
).26.
A.
Georges
, G.
Kotliar
, W.
Krauth
, and M. J.
Rozenberg
, “Dynamical mean-field theory of strongly correlated fermion systems and the limit of infinite dimensions
,” Rev. Mod. Phys.
68
(1
), 13
(1996
).27.
S. A.
Moten
, R.
Atta-Fynn
, A. K.
Ray
, and M. N.
Huda
, “Size effects on the electronic and magnetic properties of PuO2 (111) surface
,” J. Nucl. Mater.
468
, 37
–45
(2016
).28.
G.
van der Laan
, K. T.
Moore
, J. G.
Tobin
, B. W.
Chung
, M. A.
Wall
, and A. J.
Schwartz
, “Applicability of the spin-orbit sum rule for the actinide 5f states
,” Phys. Rev. Lett.
93
(9
), 097401
(2004
).29.
R.
Caciuffo
, N.
Magnani
, P.
Santini
, S.
Carretta
, G.
Amoretti
, E.
Blackburn
, M.
Enderle
, P. J.
Brown
, and G. H.
Lander
, “Anisotropic magnetic fluctuations in 3-k antiferromagnets
,” J. Magn. Magn. Mater.
310
(2
), 1698
–1702
(2007
).30.
P.
Giannozzi
and P.
Erdös
, “Theoretical analysis of the 3-k magnetic structure and distortion of uranium dioxide
,” J. Magn. Magn. Mater.
67
(1
), 75
–87
(1987
).31.
C.
Zhang
, Y.
Yang
, and P.
Zhang
, “Water dissociation on the reduced PuO2 (110) surface from first principles
,” Sci. China: Phys., Mech. Astron.
62
(10
), 107002
(2019
).32.
H. L.
Yu
, G.
Li
, H. B.
Li
, R. Z.
Qiu
, H.
Huang
, and D. Q.
Meng
, “Adsorption and dissociation of H2 on PuO2 (110) surface: A density functional theory study
,” J. Alloys Compd.
654
, 567
–573
(2016
).33.
H. L.
Yu
, T.
Tang
, S. T.
Zheng
, Y.
Shi
, R. Z.
Qiu
, W. H.
Luo
, and D. Q.
Meng
, “A theoretical study of hydrogen atoms adsorption and diffusion on PuO2 (110) surface
,” J. Alloys Compd.
666
, 287
–291
(2016
).34.
B.
Ao
, R.
Qiu
, H.
Lu
, and P.
Chen
, “Differences in the existence states of hydrogen in UO2 and PuO2 from DFT+U calculations
,” J. Phys. Chem. C
120
(33
), 18445
–18451
(2016
).35.
B.
Ao
, R.
Qiu
, G.
Zhang
, Z.
Pu
, X.
Wang
, and P.
Shi
, “Light impurity atoms as the probes for the electronic structures of actinide dioxides
,” Comput. Mater. Sci.
142
, 25
–31
(2018
).36.
T.
Bo
, J.-H.
Lan
, C.-Z.
Wang
, Y.-L.
Zhao
, C.-H.
He
, Y.-J.
Zhang
, Z.-F.
Chai
, and W.-Q.
Shi
, “First-principles study of water reaction and H2 formation on UO2 (111) and (110) single crystal surfaces
,” J. Phys. Chem. C
118
(38
), 21935
–21944
(2014
).37.
T.
Bo
, J.-H.
Lan
, Y.-L.
Zhao
, Y.-J.
Zhang
, C.-H.
He
, Z.-F.
Chai
, and W.-Q.
Shi
, “Surface properties of NpO2 and water reacting with stoichiometric and reduced NpO2 (111), (110), and (100) surfaces from ab initio atomistic thermodynamics
,” Surf. Sci.
644
, 153
–164
(2016
).38.
T.
Bo
, J.-H.
Lan
, Y.-L.
Zhao
, Y.-J.
Zhang
, C.-H.
He
, Z.-F.
Chai
, and W.-Q.
Shi
, “First-Principles study of water adsorption and dissociation on the UO2 (111), (110) and (100) surfaces
,” J. Nucl. Mater.
454
(1
), 446
–454
(2014
).39.
B. E.
Tegner
, M.
Molinari
, A.
Kerridge
, S. C.
Parker
, and N.
Kaltsoyannis
, “Water adsorption on AnO2 {111}, {110}, and {100} surfaces (An = U and Pu): A density functional theory + U study
,” J. Phys. Chem. C
121
(3
), 1675
–1682
(2017
).40.
J. M.
Flitcroft
, M.
Molinari
, N. A.
Brincat
, M. T.
Storr
, and S. C.
Parker
, “Hydride ion formation in stoichiometric UO2
,” Chem. Commun.
51
(90
), 16209
–16212
(2015
).41.
J. M.
Flitcroft
, M.
Molinari
, N. A.
Brincat
, N. R.
Williams
, M. T.
Storr
, G. C.
Allen
, and S. C.
Parker
, “The critical role of hydrogen on the stability of oxy-hydroxyl defect clusters in uranium oxide
,” J. Mater. Chem. A
6
(24
), 11362
–11369
(2018
).42.
J.
Glascott
, “A model for the initiation of reaction sites during the uranium–hydrogen reaction assuming enhanced hydrogen transport through linear oxide discontinuities
,” Philos. Mag.
94
(13
), 1393
–1413
(2014
).43.
J.
Glascott
, “A model for the initiation of reaction sites during the uranium–hydrogen reaction assuming enhanced hydrogen transport through thin areas of surface oxide
,” Philos. Mag.
94
(3
), 221
–241
(2014
).44.
M.
Fronzi
, S.
Piccinin
, B.
Delley
, E.
Traversa
, and C.
Stampfl
, “Water adsorption on the stoichiometric and reduced CeO2 (111) surface: A first-principles investigation
,” Phys. Chem. Chem. Phys.
11
(40
), 9188
–9199
(2009
).45.
J. T.
Pegg
, A. E.
Shields
, M. T.
Storr
, D. O.
Scanlon
, and N. H.
de Leeuw
, “Interaction of hydrogen with actinide dioxide (111) surfaces
,” J. Chem. Phys.
150
(13
), 134701
(2019
).46.
V. I.
Anisimov
, Strong Coulomb Correlations in Electronic Structure Calculations
(CRC Press
, 2000
).47.
J.
Heyd
, G. E.
Scuseria
, and M.
Ernzerhof
, “Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
,” J. Chem. Phys.
124
(21
), 219906
(2006
).48.
G. I.
Csonka
, J. P.
Perdew
, A.
Ruzsinszky
, P. H.
Philipsen
, S.
Lebègue
, J.
Paier
, O. A.
Vydrov
, and J. G.
Ángyán
, “Assessing the performance of recent density functionals for bulk solids
,” Phys. Rev. B
79
(15
), 155107
(2009
).49.
D.
Hait
, A.
Rettig
, and M.
Head-Gordon
, “Well-behaved vs ill-behaved density functionals for single bond dissociation: Separating success from disaster functional by functional for stretched H2
,” J. Chem. Phys.
150
(9
), 094115
(2019
).50.
G.
Henkelman
, A.
Arnaldsson
, and H.
Jónsson
, “A fast and robust algorithm for Bader decomposition of charge density
,” Comput. Mater. Sci.
36
(3
), 354
–360
(2006
).51.
W.
Tang
, E.
Sanville
, and G.
Henkelman
, “A grid-based Bader analysis algorithm without lattice bias
,” J. Phys.: Condens. Matter
21
(8
), 084204
(2009
).52.
E.
Sanville
, S. D.
Kenny
, R.
Smith
, and G.
Henkelman
, “Improved grid-based algorithm for Bader charge allocation
,” J. Comput. Chem.
28
(5
), 899
–908
(2007
).53.
A.
Horn
and H.
Lanig
, “Encyclopedia of computational chemistry
,” J. Mol. Model.
5
(9
), 141
–142
(1999
).54.
E.
Bousquet
and N.
Spaldin
, “J-dependence in the LSDA+U treatment of noncollinear magnets
,” Phys. Rev. B
82
(22
), 220402
(2010
).55.
M. T.
Suzuki
, N.
Magnani
, and P. M.
Oppeneer
, “Microscopic theory of the insulating electronic ground states of the actinide dioxides AnO2 (An = U, Np, Pu, Am, and Cm)
,” Phys. Rev. B
88
(19
), 195146
(2013
).56.
G. W.
Watson
, E. T.
Kelsey
, N. H.
de Leeuw
, D. J.
Harris
, and S. C.
Parker
, “Atomistic simulation of dislocations, surfaces and interfaces in MgO
,” J. Chem. Soc., Faraday Trans.
92
(3
), 433
–438
(1996
).57.
P. W.
Tasker
, “The structure and properties of fluorite crystal surfaces
,” J. Phys. Colloq.
41
(C6
), C6-
488
–C6-491
(1980
).58.
P. W.
Tasker
, “The stability of ionic crystal surfaces
,” J. Phys. C: Solid State Phys.
12
(22
), 4977
(1979
).59.
W.
Sun
and G.
Ceder
, “Efficient creation and convergence of surface slabs
,” Surf. Sci.
617
, 53
–59
(2013
).60.
S.
Steiner
, S.
Khmelevskyi
, M.
Marsmann
, and G.
Kresse
, “Calculation of the magnetic anisotropy with projected-augmented-wave methodology and the case study of disordered Fe1−xCox alloys
,” Phys. Rev. B
93
(22
), 224425
(2016
).61.
A. M.
Ganose
, A. J.
Jackson
, and D. O.
Scanlon
, “Sumo: Command-line tools for plotting and analysis of periodic ab initio calculations
,” J. Open Source Software
3
(28
), 717
(2018
).62.
A.
Balakrishnan
, V.
Smith
, and B.
Stoicheff
, “Dissociation energy of the hydrogen molecule
,” Phys. Rev. Lett.
68
(14
), 2149
–2152
(1992
).63.
G.
Herzberg
, “The dissociation energy of the hydrogen molecule
,” J. Mol. Spectrosc.
33
(1
), 147
–168
(1970
).64.
J. M.
Haschke
and T. H.
Allen
, “Plutonium hydride, sesquioxide and monoxide monohydride: Pyrophoricity and catalysis of plutonium corrosion
,” J. Alloys Compd.
320
(1
), 58
–71
(2001
).65.
J. M.
Haschke
, T. H.
Allen
, and J. C.
Martz
, “Oxidation kinetics of plutonium in air: Consequences for environmental dispersal
,” J. Alloys Compd.
271-273
, 211
–215
(1998
).66.
D.
Olander
, “Nuclear fuels—Present and future
,” J. Nucl. Mater.
389
(1
), 1
–22
(2009
).67.
Y.
Tanaka
, N.
Terada
, T.
Nakajima
, M.
Taguchi
, T.
Kojima
, Y.
Takata
, S.
Mitsuda
, M.
Oura
, Y.
Senba
, H.
Ohashi
, and S.
Shin
, “Incommensurate orbital modulation behind ferroelectricity in CuFeO2
,” Phys. Rev. Lett.
109
(12
), 127205
(2012
).68.
T. M.
McCleskey
, E.
Bauer
, Q.
Jia
, A. K.
Burrell
, B. L.
Scott
, S. D.
Conradson
, A.
Mueller
, L.
Roy
, X.
Wen
, G. E.
Scuseria
, and R. L.
Martin
, “Optical band gap of NpO2 and PuO2 from optical absorbance of epitaxial films
,” J. Appl. Phys.
113
(1
), 013515
(2013
).69.
P.
Erdös
, G.
Solt
, Z.
⊙ołnierek
, A.
Blaise
, and J. M.
Fournier
, “Magnetic susceptibility and the phase transition of NpO2
,” Physica B+C
102
(1
), 164
–170
(1980
).2020
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