Observation of Weakened V-V Dimers in the Monoclinic Metallic Phase of Strained VO_{2}.

Emergent order at mesoscopic length scales in condensed matter can provide fundamental insight into the underlying competing interactions and their relationship with the order parameter. Using spectromicroscopy, we show that mesoscopic stripe order near the metal-insulator transition (MIT) of strained VO_{2} represents periodic modulations in both crystal symmetry and V-V dimerization. Above the MIT, we unexpectedly find the long-range order of V-V dimer strength and crystal symmetry become dissociated beyond ≈200 nm, whereas the conductivity transition proceeds homogeneously in a narrow temperature range.

Effects of rare-earth size on the electronic structure of La1−xLuxVO3.

The electronic structure of La(1-x)Lu(x)VO(3)(x = 0, 0.2, 0.6 and 1) single crystals has been investigated using soft x-ray absorption spectroscopy, soft x-ray emission spectroscopy, and resonant soft x-ray inelastic scattering to study the effects of rare-earth size. The x-ray absorption and emission spectra at the O K-edge present a progressive evolution with R-site cation, in agreement with local spin density approximation calculations. This evolution with R, together with the temperature dependence of the O K-edge spectra, is attributed to changes in the crystal structure of La(1-x)Lu(x)VO(3). The crystal-field dd. excitations probed by resonant inelastic x-ray scattering at the V L(3)-edge exhibit an increase in energy and enhanced intensity with the decrease of R-site ionic radius, which is mainly attributed to the increased tilting magnitude of the VO(6) octahedra. Upon cooling to ~95 K, the dd* excitations are prominently enhanced in relative Intensity, in agreement with the formation of the Jahn.Teller distortion int he orbital ordering phase. Additionally, the dd* transitions of the mixed compounds are noticeably suppressed with respect to those of the pure compounds, possibly owing to the formation of C-type orbital ordering induced by large R-site size variances.

Direct observation of decoupled structural and electronic transitions and an ambient pressure monocliniclike metallic phase of VO2.

We report the simultaneous measurement of the structural and electronic components of the metal-insulator transition (MIT) of VO2 using electron and photoelectron spectroscopies and microscopies. We show that these evolve over different temperature scales, and are separated by an unusual monocliniclike metallic phase. Our results provide conclusive evidence that the new monocliniclike metallic phase, recently identified in high-pressure and nonequilibrium measurements, is accessible in the thermodynamic transition at ambient pressure, and we discuss the implications of these observations on the nature of the MIT in VO2.

Low-energy V t2g orbital excitations in NdVO3.

The electronic structure of NdVO(3) and YVO(3) has been investigated as a function of sample temperature using resonant inelastic soft x-ray scattering at the V L(3)-edge. Most of the observed spectral features are in good agreement with an atomic crystal-field multiplet model. However, a low energy feature is observed at ∼ 0.4 eV that cannot be explained by crystal-field arguments. The resonant behaviour of this feature establishes it as due to excitations of the V t(2g) states. Moreover, this feature exhibits a strong sample temperature dependence, reaching maximum intensity in the orbitally-ordered phase of NdVO(3), before becoming suppressed at low temperatures. This behaviour indicates that the origin of this feature is a collective orbital excitation, i.e. the bi-orbiton.

Resonant soft-X-ray emission as a bulk probe of correlated electron behavior in metallic SrxCa1-xVO3.

The evolution of electron correlation in SrxCa1-xVO3 has been studied using a combination of bulk-sensitive resonant soft x-ray emission spectroscopy, surface-sensitive photoemission spectroscopy, and ab initio band structure calculations. We show that the effect of electron correlation is enhanced at the surface. Strong incoherent Hubbard subbands are found to lie ∼20% closer in energy to the coherent quasiparticle features in surface-sensitive photoemission spectroscopy measurements compared with those from bulk-sensitive resonant soft x-ray emission spectroscopy, and a ∼10% narrowing of the overall bandwidth at the surface is also observed.

The band structure of WO3 and non-rigid-band behaviour in Na0.67WO3 derived from soft x-ray spectroscopy and density functional theory.

The electronic structure of single-crystal WO3 and Na0.67WO3 (a sodium-tungsten bronze) has been measured using soft x-ray absorption and resonant soft x-ray emission oxygen K-edge spectroscopies. The spectral features show clear differences in energy and intensity between WO3 and Na0.67WO3. The x-ray emission spectrum of metallic Na0.67WO3 terminates in a distinct Fermi edge. The rigid-band model fails to explain the electronic structure of Na0.67WO3 in terms of a simple addition of electrons to the conduction band of WO3. Instead, Na bonding and Na 3s-O 2p hybridization need to be considered for the sodium-tungsten bronze, along with occupation of the bottom of the conduction band. Furthermore, the anisotropy in the band structure of monoclinic γ-WO3 revealed by the experimental spectra with orbital-resolved geometry is explained via density functional theory calculations. For γ-WO3 itself, good agreement is found between the experimental O K-edge spectra and the theoretical partial density of states of O 2p orbitals. Indirect and direct bandgaps of insulating WO3 are determined from extrapolating separations between spectral leading edges and accounting for the core-hole energy shift in the absorption process. The O 2p non-bonding states show upward band dispersion as a function of incident photon energy for both compounds, which is explained using the calculated band structure and experimental geometry.

Fermi surface of an important nanosized metastable phase: Al3Li.

Nanoscale particles embedded in a metallic matrix are of considerable interest as a route towards identifying and tailoring material properties. Al-Li alloys, which form ordered nanoscale precipitates of Al(3)Li for a range of concentrations, have been deployed successfully in the aerospace industry owing to their superior strength-to-weight ratio. The precipitates are metastable and their electronic structure has so far been inaccessible through conventional techniques. Here, we take advantage of the strong positron affinity of Li to probe the Fermi surface of nanoscale Al(3)Li precipitates.

Bulk spin polarization of Co(1-x)Fe(x)S2.

We report on a new method to determine the degree of bulk spin polarization in single crystal Co(1-x)Fe(x)S2 by modeling magnetic Compton scattering with ab initio calculations. Spin-dependent Compton profiles were measured for CoS2 and Co0.9Fe0.1S2. The ab initio calculations were then refined by rigidly shifting the bands to provide the best fit between the calculated and experimental directional profiles for each sample. The bulk spin polarizations, P, corresponding to the spin-polarized density of states at the Fermi level, were then extracted from the refined calculations. The values were found to be P=-72+/-6% and P=18+/-7% for CoS2 and Co0.9Fe0.1S2, respectively. Furthermore, determinations of P weighted by the Fermi velocity (v(F) or v(F)2) were obtained, permitting a rigorous comparison with other experimental data and highlighting the experimental dependence of P on v(F).

Observation of a strongly nested Fermi surface in the shape-memory alloy Ni0.62Al0.38.

The Fermi surface topology of the shape-memory alloy Ni0.62Al0.38 has been determined using Compton scattering. A large area of this Fermi surface can be made to nest with other areas by translation through a vector of approximately 0.18[1,1,0](2pi/a), which corresponds to the wave vector associated with martensitic precursor phenomena such as phonon softening and diffuse streaking in electron diffraction patterns. This observation is compelling evidence that these phenomena are driven by the enhanced electron-lattice coupling due to the Fermi surface nesting.