Direct observation of charge ordering in magnetite using resonant multiwave x-ray diffraction

Charge disproportion at octahedral Fe sites in magnetite was observed at low temperature using two inversion-symmetry related three-wave resonant x-ray diffraction, 022-311 and 002-?3?1, near the iron K edge. Both of the three-wave cases involve the (002) forbidden-weak reflection. The self-normalized three-wave to two-wave (002) diffraction intensity ratio automatically cancels the self-absorption effect and leads to direct determination of charge disproportion for magnetite below 120 K. This approach provides a more direct and effective way for extracting charge-ordering information.     

Direct observation of charge order in triangular metallic AgNiO2 by single-crystal resonant X-ray scattering

We report resonant x-ray scattering measurements on a single crystal of the orbitally degenerate triangular metallic antiferromagnet 2H-AgNiO2 to probe the spontaneous transition to a triple-cell superstructure at temperatures below T(S)=365 K. We observe a strong resonant enhancement of the supercell reflections through the Ni K edge. The empirically extracted K-edge shift between the crystallographically distinct Ni sites of 2.5(3) eV is much larger than the value expected from the shift in final states, and implies a core-level shift of ～1 eV, thus providing direct evidence for the onset of spontaneous honeycomb charge order in the triangular Ni layers. We also provide band-structure calculations that explain quantitatively the observed edge shifts in terms of changes in the Ni electronic energy levels due to charge order and hybridization with the surrounding oxygens.     

Resonant X-ray scattering study of quadrupole-strain coupling in DyB4

X-ray and neutron scattering studies were performed on DyB4 which exhibits both a quadrupolar ordering and a macroscopic lattice distortion. A forbidden reflection at 7.792 keV near the Dy L3 absorption edge is identified as a quadrupolar ordering peak, and the quadrupolar order and a monoclinic structural distortion develop concomitantly below 12.3 K as second-order-type phase transitions. Coupling between the quadrupolar order and the strain in DyB4 is directly demonstrated by observing that both order parameters are proportional to each other.     

Direct observation of t2g orbital ordering in magnetite

Using soft-x-ray diffraction at the site-specific resonances in the Fe L2,3 edge, we find clear evidence for orbital and charge ordering in magnetite below the Verwey transition. The spectra show directly that the (001/2) diffraction peak (in cubic notation) is caused by t2g orbital ordering at octahedral Fe2+ sites and the (001) by a spatial modulation of the t2g occupation.     

Unconventional magnetic correlations in DyB2C and HoB2C

Layered borocarbides RB2C (R=Dy, Ho, and Er) have been studied by powder neutron diffraction at 2-30 K. ErB2C has two-sublattice antiferromagnetic order below T(N)=16.3 K, but DyB2C and HoB2C show a coexistence of a conventional canted k=(000) ferromagnetic structure and unconventional magnetic correlations. The k=(000) phase orders at T(c)=8.5 K (DyB2C) and 7.1 K (HoB2C), but low-Q diffraction peaks from the unconventional correlations appear above T(c) with different critical temperatures for different peaks: at 8, 10.5, and 15.7 K for HoB2C. This scattering is fitted as diffraction from a Warren-type random magnetic layer lattice and may result from quadrupolar interactions between R3+ spins.     

Orbital dynamics of the 4f shell in DyB2C2

For the first time, fluctuations in the Dy quadrupole (orbital) moment have been observed in DyB(2)C(2) using inelastic neutron scattering. The observed quasielastic response is decomposed into two components, one reflecting transitions within the doublets (narrow) and the other transitions between the doublets (broad) of the effective Dy quartet ground state. The widths of the narrow and broad components are shown to arise from fluctuations in the magnetic dipole and the electric quadrupole moments, respectively.     

Charge-orbital ordering and Verwey transition in magnetite measured by resonant soft X-ray scattering

We report experimental evidence for the charge-orbital ordering in magnetite below the Verwey transition temperature T(V). Measurements of O K-edge resonant x-ray scattering on magnetite reveal that the O 2p states in the vicinity of the Fermi level exhibit a charge-orbital ordering along the c axis with a spatial periodicity of the doubled lattice parameter of the undistorted cubic phase. Such a charge-orbital ordering vanishes abruptly above T(V) and exhibits a thermal hysteresis, correlating closely with the Verwey transition in magnetite.     

Ordered charge asphericity around dysprosium and structural deformation in DyB2C2

The orbitally ordered phase of DyB2C2 has been studied by nonresonant x-ray diffraction with high-brilliance synchrotron radiation. From the condition of diffraction, the symmetry property of the charge distribution around dysprosium has been concluded at the quadrupolar level. The quantitative inspection, furthermore, indicates that the observed signals cannot be interpreted as arising only from the 4f electrons of dysprosium responsible for the ordering; instead, the experiment can be described rather well by considering a distortion of the metaloid network concomitant with the ordering.     

Spin alignment in resonant C+O inelastic scattering

The spin alignment of the 3⁻ state (6.13 MeV) of ¹⁶O from inelastic scattering of ¹²C+¹⁶O has been measured in the energy region of known resonances around E_cm=20 MeV. The result, that the population of the m=±3 magnetic substates is enhanced on four resonances at 19.7, 20.5, 22.0 and 22.6 MeV, indicates the dominance of the aligned configuration on these resonances.     

X-Ray anomalous scattering study of a charge-ordered state in NaV2O5

Charge ordering of V4+ and V5+ in NaV2O5 has been studied by an x-ray diffraction technique using anomalous scattering near a vanadium K-absorption edge to critically enhance a contrast between the two ions. A dramatic energy dependence of the superlattice intensities is observed below T(C) = 35 K. The charge ordering pattern is the fully charged zigzag-type ladder with the unit cell 2ax2bx4c, but not the chain-type originally proposed for the spin-Peierls state. Charge disproportionation suggested in our model as the average valence V(4.5+/-delta(c)/2) is observed below T(C), showing continuous variation of delta(c) as a function of temperature.     

Direct observation of optical excitation transfer based on resonant optical near-field interaction

This article reports the direct observation of long-distance optical excitation transfer based on resonant optical near-field interactions in randomly distributed quantum dots (QDs). We fabricated optical excitation transfer paths based on randomly distributed QDs by using CdSe/ZnS core?Cshell QDs and succeeded for the first time in obtaining output signals resulting from a unidirectional optical excitation transfer length of 2.4???m. Furthermore, we demonstrate that the optical excitation transfer occurs via the resonant excited levels of the QDs with a comparative experiment using non-resonant QDs. This excitation-transfer mechanism allows for intersecting, non-interacting nano-optical wires.     

Modelling electron-N2 scattering in the resonant region

Quantum calculations of the resonant vibrational excitation of N₂ by electron impact are carried out using a model potential for exchange and correlation-polarization forces and exact static interaction. The inelastic process is treated within a coupled channel, space-frame formulation and final cross-sections are tested for convergence within less than of their values. Comparison with the experiments yields very good agreement with the latter data in the resonance region and suggests possible extension to calculations near the threshold openings for rovibrational inelastic processes induced by electron impact.     

Direct observation of tunneling in KDP using Neutron Compton scattering

Neutron Compton scattering measurements presented here of the momentum distribution of hydrogen in KH2PO4 just above and well below the ferroelectric transition temperature are sufficiently sensitive to show clearly that the proton is coherent over both sites in the high temperature phase, a result that invalidates the commonly accepted order-disorder picture of the transition. The Born-Oppenheimer potential for the hydrogen, extracted directly from data for the first time, is consistent with neutron dif-fraction data, and the vibrational spectrum is in substantial agreement with infrared absorption measurements. The measurements are sensitive enough to detect the effect of surrounding ligands on the hydrogen bond, and can be used to study the systematic effect of the variation of these ligands in other hydrogen bonded systems.