Orbital Selective Pressure-Driven Metal-Insulator Transition in FeO from Dynamical Mean-Field Theory

In this Letter we report the first LDA+DMFT (method combining Local Density Approximation with Dynamical Mean-Field Theory) results of magnetic and spectral properties calculation for paramagnetic phases of FeO at ambient and high pressures (HP). At ambient pressure (AP) calculation gave FeO as a Mott insulator with Fe 3$d$-shell in high-spin state. Calculated spectral functions are in a good agreement with experimental PES and IPES data. Experimentally observed metal-insulator transition at high pressure is successfully reproduced in calculations. In contrast to MnO and Fe$_2$O$_3$ ($d^5$ configuration) where metal-insulator transition is accompanied by high-spin to low-spin transition, in FeO ($d^6$ configuration) average value of magnetic moment $\sqrt{}$ is nearly the same in the insulating phase at AP and metallic phase at HP in agreement with X-Ray spectroscopy data (Phys. Rev. Lett. {\bf83}, 4101 (1999)). The metal-insulator transition is orbital selective with only $t_{2g}$ orbitals demonstrating spectral function typical for strongly correlated metal (well pronounced Hubbard bands and narrow quasiparticle peak) while $e_g$ states remain insulating.Comment: 4 pages, 4 figure

Metal-ligand interplay in strongly-correlated oxides: a parametrized phase diagram for pressure induced spin transitions

We investigate the magnetic properties of archetypal transition-metal oxides MnO, FeO, CoO and NiO under very high pressure by x-ray emission spectroscopy at the K\beta line. We observe a strong modification of the magnetism in the megabar range in all the samples except NiO. The results are analyzed within a multiplet approach including charge-transfer effects. The pressure dependence of the emission line is well accounted for by changes of the ligand field acting on the d electrons and allows us to extract parameters like local d-hybridization strength, O-2p bandwidth and ionic crystal field across the magnetic transition. This approach allows a first-hand insight into the mechanism of the pressure induced spin transition.Comment: 5 pages, 3 figure

Single ion implantation for single donor devices using Geiger mode detectors

Electronic devices that are designed to use the properties of single atoms such as donors or defects have become a reality with recent demonstrations of donor spectroscopy, single photon emission sources, and magnetic imaging using defect centers in diamond. Improving single ion detector sensitivity is linked to improving control over the straggle of the ion as well as providing more flexibility in lay-out integration with the active region of the single donor device construction zone by allowing ion sensing at potentially greater distances. Using a remotely located passively gated single ion Geiger mode avalanche diode (SIGMA) detector we have demonstrated 100% detection efficiency at a distance of >75 um from the center of the collecting junction. This detection efficiency is achieved with sensitivity to ~600 or fewer electron-hole pairs produced by the implanted ion. Ion detectors with this sensitivity and integrated with a thin dielectric, for example 5 nm gate oxide, using low energy Sb implantation would have an end of range straggle of <2.5 nm. Significant reduction in false count probability is achieved by modifying the ion beam set-up to allow for cryogenic operation of the SIGMA detector. Using a detection window of 230 ns at 1 Hz, the probability of a false count was measured as 1E-1 and 1E-4 for operation temperatures of 300K and 77K, respectively. Low temperature operation and reduced false, dark, counts are critical to achieving high confidence in single ion arrival. For the device performance in this work, the confidence is calculated as a probability of >98% for counting one and only one ion for a false count probability of 1E-4 at an average ion number per gated window of 0.015.Comment: 10 pages, 5 figures, submitted to Nanotechnolog

C*-Structure and K-Theory of Boutet de Monvel's Algebra

We consider the norm closure $A$ of the algebra of all operators of order and class zero in Boutet de Monvel's calculus on a manifold $X$ with boundary $Y$. We first describe the image and the kernel of the continuous extension of the boundary principal symbol to $A$. If the $X$ is connected and $Y$ is not empty, we then show that the K-groups of $A$ are topologically determined. In case the manifold, its boundary and the tangent space of the interior have torsion-free K-theory, we prove that $K_i(A/K)$ is isomorphic to the direct sum of $K_i(C(X))$ and $K_{1-i}(C_0(TX'))$, for i=0,1, with $K$ denoting the compact ideal and $TX'$ the tangent bundle of the interior of $X$. Using Boutet de Monvel's index theorem, we also prove this result for i=1 without assuming the torsion-free hypothesis. We also give a composition sequence for $A$.Comment: Final version, to appear in J. Reine Angew. Math. Improved K-theoretic result

The influence of the Jahn–Teller effect at Fe2+ on the structure of chromite at high pressure

The crystal structure of chromite FeCr2O4 was investigated to 13.7 GPa and ambient temperature with single-crystal X-ray diffraction techniques. The unit-cell parameter decreases continuously from 8.3832 (5) to 8.2398 (11) Å up to 11.8 GPa. A fit to the Birch–Murnaghan equation of state (EoS) based on the P–V data gives: K 0 = 209 (13) GPa, K′ = 4.0 (fixed), and V 0 = 588 (1) Å3. The FeO4 tetrahedra and CrO6 octahedra are compressed isotropically with pressure with their Fe–O and Cr–O bond distances decreasing from 1.996 (6) to 1.949 (7) Å and from 1.997 (3) to 1.969 (7) Å, respectively. The tetrahedral site occupied by the Fe2+ cation is more compressible than the octahedral site occupied by the Cr3+ cation. The resulting EoS parameters for the tetrahedral and the octahedral sites are K 0 = 147 (9) GPa, K′ = 4.0 (fixed), V 0 = 4.07 (1) Å3 and K 0 = 275 (24) GPa, K′ = 4.0 (fixed), V 0 = 10.42 (2) Å3, respectively. A discontinuous volume change is observed between 11.8 and 12.6 GPa. This change indicates a phase transition from a cubic (space group Fd-3 m) to a tetragonal structure (space group I41 /amd). At the phase transition boundary, the two Cr–O bonds parallel to the c-axis shorten from 1.969 (7) to 1.922 (17) Å and the other four Cr–O bonds parallel to the ab plane elongate from 1.969 (7) to 1.987 (9) Å. This anisotropic deformation of the octahedra leads to tetragonal compression of the unit cell along the c-axis. The angular distortion in the octahedron decreases continuously up to 13.7 GPa, whereas the distortion in the tetrahedron rises dramatically after the phase transition. At the pressure of the phase transition, the tetrahedral bond angles along the c-axis direction of the unit cell begin decreasing from 109.5° to 106.6 (7)°, which generates a “stretched” tetrahedral geometry. It is proposed that the Jahn–Teller effect at the tetrahedrally coordinated Fe2+ cation becomes active with compression and gives rise to the tetrahedral angular distortion, which in turn induces the cubic-to-tetragonal transition. A qualitative molecular orbital model is proposed to explain the origin and nature of the Jahn–Teller effect observed in this structure and its role in the pressure-induced phase transition

Inelastic X-ray Scattering by Electronic Excitations in Solids at High Pressure

Investigating electronic structure and excitations under extreme conditions gives access to a rich variety of phenomena. High pressure typically induces behavior such as magnetic collapse and the insulator-metal transition in 3d transition metals compounds, valence fluctuations or Kondo-like characteristics in $f$-electron systems, and coordination and bonding changes in molecular solids and glasses. This article reviews research concerning electronic excitations in materials under extreme conditions using inelastic x-ray scattering (IXS). IXS is a spectroscopic probe of choice for this study because of its chemical and orbital selectivity and the richness of information it provides. Being an all-photon technique, IXS has a penetration depth compatible with high pressure requirements. Electronic transitions under pressure in 3d transition metals compounds and $f$-electron systems, most of them strongly correlated, are reviewed. Implications for geophysics are mentioned. Since the incident X-ray energy can easily be tuned to absorption edges, resonant IXS, often employed, is discussed at length. Finally studies involving local structure changes and electronic transitions under pressure in materials containing light elements are briefly reviewed.Comment: submitted to Rev. Mod. Phy

Partitioning of the water soluble versus insoluble fraction of trace elements in the city of Santiago, Chile

The total elemental composition and the water-soluble fraction of PM10 from three different urban areas in Santiago, Chile, from downtown to the suburbs, were investigated. PM10 samples collected during the month of May (mid-autumn in the Southern Hemisphere) in 2006, 2008, 2009, and 2010 were analyzed for major and trace metals, and the partitioning between the insoluble and soluble fractions was determined for most of them. PM10 average concentrations ranged from 71 µg m–3 (Cerrillos) to 128 µg m–3 (La Pintana), which are within the seasonal ranges observed in Santiago. Twenty five major and trace elements (Fe, Al, Ca, K, Mg, P, Pb, S, Ti, Mn, Cu, Zn, Ba, Zr, Cr, As, Sn, Sb, Ni, V, Li, Co, Cd, La, and Rb) were determined in the present study. Ba, Sb, Cd, As, and Zn, with proportions in the soluble fraction varying from 50% to 98%, were the most soluble elements. On the contrary, the less soluble trace elements were Ti, Sn, Pb, and Cr. Most of the high-solubility trace metals are strongly linked to non-exhaust traffic emissions, as well as to certain industrial sources. Our results evidence the significant amount of soluble trace elements in Santiago’s urban atmosphere classified as toxic and/or carcinogenic, thus suggesting a non-negligible health impact

Experimental and theoretical evidence for pressure-induced metallization in FeO with the rock-salt type structure

Electrical conductivity of FeO was measured up to 141 GPa and 2480 K in a laserheated diamond-anvil cell. The results show that rock-salt (B1) type structured FeO metallizes at around 70 GPa and 1900 K without any structural phase transition. We computed fully self-consistently the electronic structure and the electrical conductivity of B1 FeO as a function of pressure and temperature, and found that although insulating as expected at ambient condition, B1 FeO metallizes at high temperatures, consistent with experiments. The observed metallization is related to spin crossover

High P-T Raman study of transitions in relaxor multiferroic Pb(Fe0.5Nb0.5)O-3

The vibrational and structural properties of Pb(Fe0.5Nb0.5)O-3 have been investigated using Raman spectroscopy up to 40GPa at 300K and from 300 to 415K at selected pressures. The measurements reveal three phase transitions, at 5.5, 8.7, and 24GPa at room temperature. The temperature dependences of the spectra indicate transitions at 1.5GPa, at 335 and 365K. The results are consistent with the appearance of an intermediate tetragonal P4mm phase between the ferroelectric R3m and paraelectric Pm-3m phases. A P-T phase diagram is proposed that allows further insight into the magnetoelectric coupling present in this material. Copyright (c) 2015 John Wiley &amp; Sons, Ltd.</p