The hexavalent and heptavalent sodium neptunate compounds Na4NpO5 and Na5NpO6 have been investigated using X-ray powder diffraction, Mössbauer spectroscopy, magnetic susceptibility, and specific heat measurements. Na4NpO5 has tetragonal symmetry in the space group I4/m, while Na5NpO6 adopts a monoclinic unit cell in the space group C2/m. Both structures have been refined for the first time using the Rietveld method. The valence states of neptunium in these two compounds, i.e., Np(VI) and Np(VII), respectively, have been confirmed by the isomer shift values of their Mössbauer spectra. The local structural properties obtained from the X-ray refinements have also been related to the quadrupole coupling constants and asymmetry parameters determined from the Mössbauer studies. The absence of magnetic ordering has been confirmed for Na4NpO5. However, specific heat measurements at low temperatures have suggested the existence of a Schottky-type anomaly at around 7 K in this Np(VI) phase.
The physical and chemical properties at low temperatures of hexavalent disodium neptunate α-Na2NpO4 are investigated for the first time in this work using Mössbauer spectroscopy, magnetization, magnetic susceptibility, and heat capacity measurements. The Np(VI) valence state is confirmed by the isomer shift value of the Mössbauer spectra, and the local structural environment around the neptunium cation is related to the fitted quadrupole coupling constant and asymmetry parameters. Moreover, magnetic hyperfine splitting is reported below 12.5 K, which could indicate magnetic ordering at this temperature. This interpretation is further substantiated by the existence of a λ-peak at 12.5 K in the heat capacity curve, which is shifted to lower temperatures with the application of a magnetic field, suggesting antiferromagnetic ordering. However, the absence of any anomaly in the magnetization and magnetic susceptibility data shows that the observed transition is more intricate. In addition, the heat capacity measurements suggest the existence of a Schottky-type anomaly above 15 K associated with a low-lying electronic doublet found about 60 cm(-1) above the ground state doublet. The possibility of a quadrupolar transition associated with a ground state pseudoquartet is thereafter discussed. The present results finally bring new insights into the complex magnetic and electronic peculiarities of α-Na2NpO4.
α-Na3NpO4 and α-Na3PuO4 exhibit an orthorhombic structure (Z = 8), in space group Fmmm, with lattice parameters a = 13.352(2) Å, b = 9.629(2) Å, and c = 6.673(2) Å for the neptunium compound, and a = 13.302(2) Å, b = 9.634(2) Å, and c = 6.651(2) Å for the plutonium analogue. The corresponding structure has been solved ab initio as no structural analogue could be found in the literature. The pentavalent state of neptunium has moreover been confirmed by (237)Np Mössbauer spectroscopy, and the local structural properties inferred from the X-ray Rietveld refinement have been related to the fitted quadrupole coupling constant and asymmetry parameters. The existence of a low temperature metastable m phase of Na3NpO4 and Na3PuO4, of the NaCl type, has also been suggested.
Low temperature Co K-edge x-ray magnetic circular dichroism spectra at different field cooling conditions were recorded to study the imprinted magnetization in antiferromagnetic (AFM) Co doped ZnO (Co:ZnO) films which manifests itself in a vertical exchange bias effect. Co:ZnO films with 50% and 60% doping concentrations were investigated to provide a high degree of pinned magnetic moments. The measurements reveal a change at the main absorption energy of the spectra, while the signal obtained at the pre-edge stays unaffected by the cooling conditions. Therefore, the pinned uncompensated AFM moments, resulting in an imprinted magnetization, are predominantly of orbital character and are independent of ferromagnetic layers.
A previously unknown neptunium-transition-metal binary compound Np 2 Co 17 has been synthesized and characterized by means of powder x-ray diffraction, 237 Np Mössbauer spectroscopy, superconducting-quantuminterference-device magnetometry, and x-ray magnetic circular dichroism (XMCD). The compound crystallizes in a Th 2 Ni 17 -type hexagonal structure with room-temperature lattice parameters a = 8.3107(1)Å and c = 8.1058(1)Å. Magnetization curves indicate the occurrence of ferromagnetic order below T C > 350 K. Mössbauer spectra suggest a Np 3+ oxidation state and give an ordered moment of μ Np = 1.57(4) μ B and μ Np = 1.63(4) μ B for the Np atoms located, respectively, at the 2b and 2d crystallographic positions of the P 6 3 /mmc space group. Combining these values with a sum-rule analysis of the XMCD spectra measured at the neptunium M 4,5 absorption edges, one obtains the spin and orbital contributions to the site-averaged Np moment [μ S = −1.88(9) μ B , μ L = 3.48(9) μ B ]. The ratio between the expectation value of the magnetic-dipole moment and the spin magnetic moment (m md /μ S = +1.36) is positive as predicted for localized 5f electrons and lies between the values calculated in intermediate-coupling (IC) and jj approximations. The expectation value of the angular part of the spin-orbit-interaction operator is in excellent agreement with the IC estimate. The ordered moment averaged over the four inequivalent Co sites, as obtained from the saturation value of the magnetization, is μ Co 1.6 μ B . The experimental results are discussed against the predictions of first-principles electronic-structure calculations based on the spin-polarized local-spin-density approximation plus the Hubbard interaction.
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