Density Functional Theory Studies of the Electronic Structure of Solid State Actinide Oxides

Wen, Xiaodong; Martin, Richard L.; Henderson, Thomas M.; Scuseria, Gustavo E.

doi:10.1021/cr300374y

Cited by 208 publications

(221 citation statements)

References 224 publications

(357 reference statements)

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“…The FEFF calculations (Fig. 8(c)) get a slightly smaller gap for that transition (6.5 eV), but as shown in the review 58 , there are many calculations with this transition varying from 5 − 10 eV.…”

Section: Valence Band Resonant Inelastic X-ray Scattering (Rixs)mentioning

confidence: 85%

Resonant x-ray spectroscopy of uranium intermetallics at the M4,5 edges of uranium

et al. 2017

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We present resonant x-ray emission spectroscopic (RXES) data from the uranium intermetallics UPd3, USb, USn3 and URu2Si2 at the U M4,5 edges and compare the data to those from the well-localized 5f 2 semiconductor UO2. The technique is especially sensitive to any oxidation of the surface, and this was found on the USb sample, thus preventing a good comparison with a material known to be 5f 3 . We have found a small energy shift between UO2 and UPd3, both known to have localized 5f 2 configurations, which we ascribe to the effect of conduction electrons in UPd3. The spectra from UPd3 and URu2Si2 are similar, strongly suggesting a predominant 5f 2 configuration for URu2Si2. The valence-band resonant inelastic x-ray scattering (RIXS) provides information on the U P3 transitions (at about 18 eV) between the U 5f and U 6p states, as well as transitions of between 3 and 7 eV from the valence band into the unoccupied 5f states. These transitions are primarily involving mixed ligand states (O 2p or Pd, Ru 4d) and U 5f states. Calculations are able to reproduce both these low-energy transitions reasonably well.

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Section: Valence Band Resonant Inelastic X-ray Scattering (Rixs)mentioning

confidence: 85%

Resonant x-ray spectroscopy of uranium intermetallics at the M4,5 edges of uranium

et al. 2017

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“…Adsorption energies of water on differently oriented uranium dioxide planes were calculated. 14, 15,16 The work on the study of the electronic structure of uranium and its alloys [17][18][19][20][21] and oxides UO 2+x (x≤0 and x≥0) employed theoretical calculation results, [22][23][24][25][26][27][28][29][30][31][32][33][34] photoelectron spectroscopy (PES) [35][36][37][38][39][40][41] and X-ray photoelectron spectroscopy (XPS) widely. 38,[42][43][44][45][46][47][48][49][50][51][52][53][54][55] These techniques were used to study films on various substrates.…”

Section: Introductionmentioning

confidence: 99%

XPS Study of Ion Irradiated and Unirradiated UO₂ Thin Films

et al. 2016

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XPS determination of the oxygen coefficient k O =2+x and ionic (U 4+ , U 5+ and U 6+ ) composition of oxides UO 2+x formed on the surfaces of differently oriented (hkl) planes of thin UO 2 films on LSAT (Al 10 La 3 O 51 Sr 14 Ta 7 ) and YSZ (yttria-stabilized zirconia) substrates was performed. The U 4f and O 1s core-electron peak intensities as well as the U 5f relative intensity before and after the 129 Xe 23+ and 238 U 31+ irradiations were employed. It was found that the presence of uranium dioxide film in air results in formation of oxide UO 2+x on the surface with mean oxygen coefficients k O in the range 2.07-2.11 on LSAT and 2.17-2.23 on YSZ substrates. These oxygen coefficients depend on the substrate and weakly on the crystallographic orientation.On the basis of the spectral parameters it was established that uranium dioxide films AP2,3 on the LSAT substrates have the smallest k O values, and from the XRD and EBSD results it follows that these samples have a regular monocrystalline structure. The XRD and EBSD results indicate that samples AP5-7 on the YSZ substrates have monocrystalline structure, however, they have the highest k O values. The observed difference in the k O values, probably, caused by the different nature of the substrates: the YSZ substrates provide 6.4% compressive strain, whereas (001) LSAT substrates result only in 0.03% tensile strain in the UO 2 films.129 Xe 23+ irradiation (92 MeV, 4.8 × 10 15 ions/cm 2 ) of uranium dioxide films on the LSAT substrates was shown to destroy both long range ordering and uranium close environment, which results in increase of uranium oxidation state and regrouping of oxygen ions in uranium close environment. 238 U 31+ (110 MeV, 5 × 10 10 , 5 × 10 11 , 5 × 10 12 ions/cm 2 ) irradiations of uranium dioxide films on the YSZ substrates were shown to form the lattice damage only with partial destruction of the long range ordering.3

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“…[8][9][10] Today, a large body of evidence has been gathered that supports 5f and 6d orbitals being involved in covalent bonding to a degree that is similar to that of d-orbitals in transition-metal complexes. [1-3, 6, 7, 9] In fact, there has been tantalizing evidence since at least the 1960s, and less definitive suggestions since the 1950s that 5f orbitals for actinides are involved in bonding in some compounds.…”

mentioning

confidence: 99%

Chirality and Polarity in the f‐Block Borates M₄[B₁₆O₂₆(OH)₄(H₂O)₃Cl₄] (M=Sm, Eu, Gd, Pu, Am, Cm, and Cf)

Polinski¹,

Pace²,

Stritzinger³

et al. 2014

Chemistry A European J

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The reactions of trivalent lanthanides and actinides with molten boric acid in high chloride concentrations result in the formation of M4[B16O26(OH)4(H2O)3Cl4] (M = Sm, Eu, Gd, Pu, Am, Cm, Cf). This cubic structure type is remarkably complex and displays both chirality and polarity. The polymeric borate network forms helical features that are linked via two different types of nine-coordinate f-element environments. The f-f transitions are unusually intense and result in dark coloration of these compounds with actinides.

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Density Functional Theory Studies of the Electronic Structure of Solid State Actinide Oxides

Cited by 208 publications

References 224 publications

Resonant x-ray spectroscopy of uranium intermetallics at the M4,5 edges of uranium

Resonant x-ray spectroscopy of uranium intermetallics at the M4,5 edges of uranium

XPS Study of Ion Irradiated and Unirradiated UO₂ Thin Films

Chirality and Polarity in the f‐Block Borates M₄[B₁₆O₂₆(OH)₄(H₂O)₃Cl₄] (M=Sm, Eu, Gd, Pu, Am, Cm, and Cf)

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Density Functional Theory Studies of the Electronic Structure of Solid State Actinide Oxides

Cited by 208 publications

References 224 publications

Resonant x-ray spectroscopy of uranium intermetallics at the M4,5 edges of uranium

Resonant x-ray spectroscopy of uranium intermetallics at the M4,5 edges of uranium

XPS Study of Ion Irradiated and Unirradiated UO2 Thin Films

Chirality and Polarity in the f‐Block Borates M4[B16O26(OH)4(H2O)3Cl4] (M=Sm, Eu, Gd, Pu, Am, Cm, and Cf)

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XPS Study of Ion Irradiated and Unirradiated UO₂ Thin Films

Chirality and Polarity in the f‐Block Borates M₄[B₁₆O₂₆(OH)₄(H₂O)₃Cl₄] (M=Sm, Eu, Gd, Pu, Am, Cm, and Cf)