Atomic and itinerant effects at the transition metal x-ray absorption K-pre-edge exemplified in the case of V2_2O3_3

X-ray absorption spectroscopy is a well established tool for obtaining information about orbital and spin degrees of freedom in transition metal- and rare earth-compounds. For this purpose usually the dipole transitions of the L- (2p to 3d) and M- (3d to 4f) edges are employed, whereas higher order transitions such as quadrupolar 1s to 3d in the K-edge are rarely studied in that respect. This is due to the fact that usually such quadrupolar transitions are overshadowed by dipole allowed 1s to 4p transitions and, hence, are visible only as minor features in the pre-edge region. Nonetheless, these features carry a lot of valuable information, similar to the dipole L-edge transition, which is not accessible in experiments under pressure due to the absorption of the diamond anvil pressurecell. We recently performed a theoretical and experimental analysis of such a situation for the metal insulator transition of (V(1-x)Crx)2O3. Since the importance of the orbital degrees of freedom in this transition is widely accepted, a thorough understanding of quadrupole transitions of the vanadium K-pre-edge provides crucial information about the underlying physics. Moreover, the lack of inversion symetry at the vanadium site leads to onsite mixing of vanadium 3d- and 4p- states and related quantum mechanical interferences between dipole and quadrupole transitions. Here we present a theoretical analysis of experimental high resolution x-ray absorption spectroscopy at the V pre-K edge measured in partial fluorescence yield mode for single crystals. We carried out density functional as well as configuration interaction calculations in order to capture effects coming from both, itinerant and atomic limits

Inequivalent routes across the Mott transition in V2O3 explored by X-ray absorption

The changes in the electronic structure of V2O3 across the metal-insulator transition induced by temperature, doping and pressure are identified using high resolution x-ray absorption spectroscopy at the V pre K-edge. Contrary to what has been taken for granted so far, the metallic phase reached under pressure is shown to differ from the one obtained by changing doping or temperature. Using a novel computational scheme, we relate this effect to the role and occupancy of the a1g orbitals. This finding unveils the inequivalence of different routes across the Mott transition in V2O

A Microscopic View on the Mott transition in Chromium-doped V2O3

V2O3 is the prototype system for the Mott transition, one of the most fundamental phenomena of electronic correlation. Temperature, doping or pressure induce a metal to insulator transition (MIT) between a paramagnetic metal (PM) and a paramagnetic insulator (PI). This or related MITs have a high technological potential, among others for intelligent windows and field effect transistors. However the spatial scale on which such transitions develop is not known in spite of their importance for research and applications. Here we unveil for the first time the MIT in Cr-doped V2O3 with submicron lateral resolution: with decreasing temperature, microscopic domains become metallic and coexist with an insulating background. This explains why the associated PM phase is actually a poor metal. The phase separation can be associated with a thermodynamic instability near the transition. This instability is reduced by pressure which drives a genuine Mott transition to an eventually homogeneous metallic state.Comment: Paper plus supplementary materia

Direct observation of delithiation as the origin of analog memristance in LixNbO2

The discovery of analog LixNbO2 memristors revealed a promising new memristive mechanism wherein the diffusion of Li+ rather than O2- ions enables precise control of the resistive states. However, directly correlating lithium concentration with changes to the electronic structure in active layers remains a challenge and is required to truly understand the underlying physics. Chemically delithiated single crystals of LiNbO2 present a model system for correlating lithium variation with spectroscopic signatures from operando soft x-ray spectroscopy studies of device active layers. Using electronic structure modeling of the x-ray spectroscopy of LixNbO2 single crystals, we demonstrate that the intrinsic memristive behavior in LixNbO2 active layers results from field-induced degenerate p-type doping. We show that electrical operation of LixNbO2-based memristors is viable even at marginal Li deficiency and that the analog memristive switching occurs well before the system is fully metallic. This study serves as a benchmark for material synthesis and characterization of future LixNbO2-based memristor devices and suggests that valence change switching is a scalable alternative that circumvents the electroforming typically required for filamentary-based memristors

Ultrafast evolution and transient phases of a prototype out-of-equilibrium Mott-Hubbard material

The study of photoexcited strongly correlated materials is attracting growing interest since their rich phase diagram often translates into an equally rich out-of-equilibrium behaviour. With femtosecond optical pulses, electronic and lattice degrees of freedom can be transiently decoupled, giving the opportunity of stabilizing new states inaccessible by quasi-adiabatic pathways. Here we show that the prototype Mott-Hubbard material V2O3 presents a transient non-thermal phase developing immediately after ultrafast photoexcitation and lasting few picoseconds. For both the insulating and the metallic phase, the formation of the transient configuration is triggered by the excitation of electrons into the bonding a1g orbital, and is then stabilized by a lattice distortion characterized by a hardening of the A1g coherent phonon, in stark contrast with the softening observed upon heating. Our results show the importance of selective electron-lattice interplay for the ultrafast control of material parameters, and are relevant for the optical manipulation of strongly correlated systems. \ua9 The Author(s) 2017

Prevalence of Coxielle Burnetii anbitodies in Danish Dairy herds

<p>Abstract</p> <p>During recent years in Denmark higher rates of antibodies to <it>Coxiella burnetii </it>have been detected in animals and humans than previously reported. A study based on bulk tank milk samples from 100 randomly selected dairy herds was performed to estimate the prevalence and geographical distribution of antibody positive dairy herds. Using the CHEKIT Q-Fever Antibody ELISA Test Kit (IDEXX), the study demonstrated a prevalence of 59% antibody positive herds, 11% antibody intermediate herds and 30% antibody negative herds based on the instructions provided by the manufacturer. The geographical distribution does not indicate a relationship between the regional density of dairy farms and the prevalence of antibody positive dairy farms. The result supports the hypothesis of an increase in the prevalence of positive dairy herds compared to previous years.</p

Prevalence of Coxiella burnetii in clinically healthy German sheep flocks

<p>Abstract</p> <p>Background</p> <p>Current epidemiological data on the situation of <it>Coxiella (C.) burnetii </it>infections in sheep are missing, making risk assessment and the implementation of counteractive measures difficult. Using the German state of Thuringia as a model example, the estimated sero-, and antigen prevalence of <it>C. burnetii </it>(10% and 25%, respectively) was assessed at flock level in 39/252 randomly selected clinically healthy sheep flocks with more than 100 ewes and unknown abortion rate.</p> <p>Results</p> <p>The CHECKIT™ Q-fever Test Kit identified 11 (28%) antibody positive herds, whereas real-time PCR revealed the presence of <it>C. burnetii </it>DNA in 2 (5%) of the flocks. Multiple-locus variable number of tandem repeats analysis of 9 isolates obtained from one flock revealed identical profiles. All isolates contained the plasmid QpH1.</p> <p>Conclusions</p> <p>The results demonstrate that <it>C. burnetii </it>is present in clinically inconspicuous sheep flocks and sporadic flare-ups do occur as the notifications to the German animal disease reporting system show. Although <it>C. burnetii </it>infections are not a primary veterinary concern due to the lack of significant clinical impact on animal health (with the exception of goats), the eminent zoonotic risk for humans should not be underestimated. Therefore, strategies combining the interests of public and veterinary public health should include monitoring of flocks, the identification and culling of shedders as well as the administration of protective vaccines.</p