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Register a new userGroundstate electronic structure of actinide carbides and nitrides
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The self-interaction corrected (SIC) local spin-density approximation (LSD) is used to investigate the groundstate valency configuration of the actinide ions in the actinide mono-carbides, AC (A = U, Np, Pu, Am, Cm), and the actinide mono-nitrides, AN. The electronic structure is characterized by a gradually increasing degree of f-electron localization from U to Cm, with the tendency towards localization being slightly stronger in the (more ionic) nitrides compared to the (more covalent) carbides. The itinerant band-picture is found to be adequate for UC and acceptable for UN, whilst a more complex manifold of competing localized and delocalized f-electron configurations underlies the groundstates of NpC, PuC, AmC, NpN, and PuN. The fully localized 5f-electron configuration is realized in CmC (f7), CmN (f7), and AmN (f6). The observed sudden increase in lattice parameter from PuN to AmN is found to be related to the localization transition. The calculated valence electron densities of states are in good agreement with photoemission data.
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By means of first-principles calculations, the structural stability, mechanical properties and electronic structure of the newly synthesized incompressible Re2C, Re2N, Re3N and an analogous compound Re3C have been investigated. Our results agree well with the available experimental and theoretical data. The proposed Re3C is shown to be energetically, mechanically and dynamically stable and also incompressible. Furthermore, it is suggested that the incompressibility of these compounds is originated from the strong covalent bonding character with the hybridization of 5d orbital of Re and the 2p orbital of C or N, and a zigzag topology of interconnected bonds, e.g., Re-Re, Re-C or Re-N bonding.
The ground state electronic structures of the actinide oxides AO, A2O3 and AO2 (A=U, Np, Pu, Am, Cm, Bk, Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density (SIC-LSD) approximation. Emphasis is put on the degree of f-electron localization, which for AO2 and A2O3 is found to follow the stoichiometry, namely corresponding to A(4+) ions in the dioxide and A(3+) ions in the sesquioxides. In contrast, the A(2+) ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reduction of the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onwards. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground state valency agrees with the nominal valency expected from a simple charge counting.
In comparison to 3d or 4f metals, magnetism in actinides remains poorly understood due to experimental complications and the exotic behavior of the 5f states. In particular, plutonium metal is most especially vexing. Over the last five decades theories proposed the presence of either ordered or disordered local moments at low temperatures. However, experiments such as magnetic susceptibility, electrical resistivity, nuclear magnetic resonance, specific heat, and elastic and inelastic neutron scattering show no evidence for ordered or disordered magnetic moments in any of the six phases of plutonium. Beyond plutonium, the magnetic structure of other actinides is an active area of research given that temperature, pressure, and chemistry can quickly alter the magnetic structure of the 5f states. For instance, curium metal has an exceedingly large spin polarization that results in a total moment of about 8 Bohr magneton/atom, which influences the phase stability of the metal. Insight in the actinide ground state can be obtained from core-level x-ray absorption spectroscopy (XAS) and electron energy-loss spectroscopy (EELS). A sum rule relates the branching ratio of the core-level spectra measured by XAS or EELS to the expectation value of the angular part of the spin-orbit interaction.
We have investigated by means of high-pressure x-ray diffraction the structural stability of Pd2Mo3N, Ni2Mo3C0.52N0.48, Co3Mo3C0.62N0.38, and Fe3Mo3C. We have found that they remain stable in their ambient-pressure cubic phase at least up to 48 GPa. All of them have a bulk modulus larger than 330 GPa, being the least compressible material Fe3Mo3C, B0 = 374(3) GPa. In addition, apparently a reduction of compressibility is detected as the carbon content increased. The equation of state for each material is determined. A comparison with other refractory materials indicates that interstitial nitrides and carbides behave as ultra-incompressible materials.
We report nonresonant inelastic x-ray scattering from the semi-core 5d levels of several actinide compounds. Dipole-forbidden, high-multipole features form a rich bound-state spectrum dependent on valence electron configuration and spin-orbit and Coulomb interactions. Cross-material comparisons, together with the anomalously high Coulomb screening required for agreement between atomic multiplet theory and experiment, demonstrate sensitivity to the neighboring electronic environment, such as is needed to address long-standing questions of electronic localization and bonding in 5f compounds.
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