Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics

Booth, C. H.; Jiang, Yu; Wang, D.L.; Mitchell, Jeanette; Tobash, Paul H.; Bauer, E. D.; Wall, M. A.; Allen, P. G.; Sokaras, Dimosthenis; Nordlund, Dennis; Weng, Tsu Chien; Torrez, Michael A.; Sarrao, J. L.

doi:10.1073/pnas.1200725109

Cited by 99 publications

(104 citation statements)

References 47 publications

(52 reference statements)

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“…1A of Ref. 25. The intermediate state, as shown in this figure, involves a hole in the 3d core shell, with the emission to the ground state then filling the 2p core hole.…”

Section: A Overview Of Spectroscopymentioning

confidence: 99%

“…Such maps are standard for these experiments and are shown in Ref. [23][24][25][26], and 28. All spectra we have taken are similar to these data.…”

Section: B Resonant X-ray Emission Datamentioning

confidence: 99%

“…We have chosen not to analyze these data with Gaussian curves, as done by Booth et al [25][26][27] as the RXES is a two-step process and involves transitions from the ground to the excited states and from the excited to the final states. Additionally, the conclusions are not substantially different from those given after analyzing Fig.…”

Section: Cuts At Constant Incident Energymentioning

confidence: 99%

“…6, is also a useful way to present the data. Booth et al [25][26][27] have used these types of cuts in their analysis to obtain the 5f count in a number of different actinide compounds at the U L 3 edge.…”

Section: Cuts At Constant Incident Energymentioning

confidence: 99%

“…Booth et al [25][26][27] have presented RXES data at the L 3 edge on a number of actinide intermetallic compounds showing two interesting developments. First, that the edge position (i.e.…”

Section: Introductionmentioning

confidence: 99%

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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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“…1A of Ref. 25. The intermediate state, as shown in this figure, involves a hole in the 3d core shell, with the emission to the ground state then filling the 2p core hole.…”

Section: A Overview Of Spectroscopymentioning

confidence: 99%

“…Such maps are standard for these experiments and are shown in Ref. [23][24][25][26], and 28. All spectra we have taken are similar to these data.…”

Section: B Resonant X-ray Emission Datamentioning

confidence: 99%

Section: Cuts At Constant Incident Energymentioning

confidence: 99%

Section: Cuts At Constant Incident Energymentioning

confidence: 99%

“…Booth et al [25][26][27] have presented RXES data at the L 3 edge on a number of actinide intermetallic compounds showing two interesting developments. First, that the edge position (i.e.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

et al. 2017

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Plutonium and Plutonium Compounds

Clark

Freibert

Jarvinen

2017

Kirk-Othmer Encyclopedia of Chemical Technology

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The discovery of plutonium, its economic and military importance, sources, production, and nuclear properties are reviewed. The economic aspects of weapons‐grade and reactor‐grade plutonium are outlined. The preparation and properties of plutonium metal and its alloys are discussed in detail. A presentation of the physical and chemical properties of atomic plutonium and stable plutonium ions is given. The complexation and hydrolysis properties of these ions are recapitulated. Analytical chemistry, separations technology, and metallurgy (including pyrometallurgical processing) are described. There is a brief treatment of storage and disposal of excess weapons plutonium. The chemistry of several classes of plutonium compounds is described: oxides, halides, oxyhalides, hydrides, carbides, silicides, nitrides, sulfides, and oxalates. The article concludes with a treatment of environmental, health, and safety aspects of plutonium.

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Localization‐vs‐Delocalization of 5f Orbitals in Superatom Systems

Jiang

Wang

2018

Advcd Theory and Sims

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A long-standing debate on the system containing the actinide element is the extent of localization and participation of the 5f orbitals in chemical bonding across the actinide series. Here, we illuminate that the 5f orbitals have both dual nature in superatomic bonding for protactinium, uranium, neptunium, and plutonium using density functional theory. Electronic structure analysis reveals that the partial 5f electrons are active and could be preferentially excited to 6d shells to satisfy jelliumic bonding of the 18-electron rule (1S 2 1P 6 1D 10 ). In contrast, the extra 5f electrons are more localized for neptunium and plutonium compared with protactinium and uranium, and present antiferromagnetic and ferromagnetic couplings for the spin arrangements between actinide atoms and confined gold clusters, and largely localized at the actinide atom. This work offers not only a new recipe for breeding magnetic superatoms, but also is very promising for the designing of superconducting materials and heavy-fermion systems.For a long time, substantial attention has been focused on systems containing the actinide (An) elements. [1][2][3][4] One of the main reasons is that the 5f orbitals can exhibit localization like the 4f orbitals in the lanthanide series, or delocalization (participation) like the d orbitals in the transition metals, or both in the chemical bonding. In fact, the competition has resulted in multiple complicated ground states and phases in compounds and alloy systems. [5,6] Currently, although the degree of localization of 5f electrons has been recognized as the dominant factor in determining the magnetic and electronic properties of the materials, [7,8] experimental methods for measuring the occupancy of 5f electron are still very unsuccessful though some exceptions exist. Therefore, an equally important task is to explore simplified superatomic models containing actinide elements to understand the origin of their properties and enhanced stability.Currently, there are a number of electron counting rules in cluster science that can be effectively utilized in the design and synthesis of materials. [9][10][11][12][13] Among them, 18-electron rule, which is a conceptual extension to the octet rule by the insertion of a metal element with d valence electrons into the closed shell s 2 p 6 (eight electrons), has been regarded as cornerstone for understanding and explaining the transition-metal (especially for the gold clusters) structural stability and physicochemical properties. [14,15] For example, the icosahedral W/Mo@Au 12 cluster was confirmed by theoretical [16] and experimental [17] works, which stability can be attributed to and the 18-electron rule and the strong relativistic effects. Furthermore, the study of M@Au n (M: metal atom of VIIA-IA group; n = 8-17) clusters have shown that at n = 14, the gold-covered bimetallic cluster can achieve the highest binding energy per atom and gap between highest occupied molecular orbital and lowest unoccupied molecular orbital. [18] Therefore, as an important al...

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Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics

Cited by 99 publications

References 47 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

Plutonium and Plutonium Compounds

Localization‐vs‐Delocalization of 5f Orbitals in Superatom Systems

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