M. Sikora

Cr local environment by valence-to-core X-ray emission spectroscopy.

Valence-to-core X-ray emission spectra have been measured for a number of chromium compounds such as oxides, carbides, borides, nitrides, phosphides etc. The experimental spectra are in good agreement with the calculated ones. They form the basis for a detailed analysis of the first coordination shell of Cr. The unique application of this technique for material chemistry and environmental science is illustrated by two very different examples. In the former case the presence of Cr–C bonds in the bulk structure of electrochemically deposited amorphous chromium coatings was confirmed. In the latter one we have shown that a contaminated soil sample most probably contains Cr carbides and/or phosphides from anthropogenic origin.

Evidence of unquenched Re orbital magnetic moment in AA′FeReO6 double perovskites

Spin and orbital magnetic moments of rhenium in AA′FeReO6 double perovskites (A,A′=Ba, Sr, and Ca) have been directly probed employing x-ray magnetic circular dichroism at the Re L2,3 edges. A considerable orbital magnetic moment is observed in all the compounds studied, which confirm theoretical predictions of unquenched Re orbital moment despite its octahedral coordination. Relative orbital-to-spin moment ratio alters with lattice distortion from mL∕mS=−0.285to−0.337 from Ba2FeReO6 to Ca2FeReO6, respectively. Moreover, the spin moment of Re ion scales with Curie temperature, the most relevant property in spin electronics application of the compounds studied.

Magnetoresistance in FeCoZr–Al2O3 nanocomposite films containing ‘metal core–oxide shell’ nanogranules

Temperature and magnetic field dependences of electrical conductivity are systematically studied in granular films (Fe45Co45Zr10)x(Al2O3)100?x (28???x???64) containing crystalline metallic ?-FeCo-based nanoalloy cores encapsulated in an amorphous oxide shell embedded in an amorphous Al2O3 matrix. Formation of ?metallic core?oxide shell? nanogranules is confirmed by transmission electron microscopy (TEM) and HRTEM. The structure of core and shell is governed with the difference in the oxidation states of Fe and Co ions investigated with EXAFS, XANES and M?ssbauer spectroscopy. A considerable negative magnetoresistance (MR) effect of spin-dependent nature is observed in the whole range of x values. Its increase with decreasing temperature is correlated with the magnetic saturation of superparamagnetic metallic nanogranules. The enhanced MR effect in ?core?shell? granular films is related to the percolation of oxide shells and their influence through spin filtering processes. A considerable high field MR at low temperatures and the resulting deviation of MR and squared magnetization are attributed to a magnetic randomness and/or strong magnetic anisotropy of the magnetic oxide shell.

Exploring the formation of 3D ferromagnetic cyano-bridged CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2x}·yH2O networks

Two novel non-stoichiometric 3D cyano-bridged coordination networks of general formula CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2x}·yH2O were obtained according to two different synthetic strategies. The heterogeneous reaction between solid 2D cyano-bridged network (dienH3){CuII[WV(CN)8]}3·4H2O (1) (dienH33+ = protonated diethylenetriamine) and an aqueous solution of DyIII(NO3)3 results in the removal of dienH33+ cations and the formation of a 3D cyano-bridged CuII2.44{CuII4[WV(CN)8]3.12[WIV(CN)8]0.88}·5H2O (2) network. The direct combination of [CuII(H2O)6]2+ and [WV(CN)8]3− in aqueous media leads to the structurally related CuII2.97{CuII4[WV(CN)8]2.06[WIV(CN)8]1.94}·4H2O (3) assembly. The assemblies 2 and 3 were characterised by X-ray powder diffraction along with IR, X-ray absorption spectroscopy (XAS), proton induced X-ray emission (PIXE) and magnetic measurements. 2 and 3 crystallise in a tetragonal system, space group I4/mmm with cell parameters a = b = 7.2695(9) A; c = 28.268(5) A; Z = 2 (2) and a = b = 7.2858(9) A, c = 28.282(5) A, Z = 2 (3). Both networks are characterised by the increase of TC from 33 K to 40 K and coercivity from 0.2 to 2–2.5 kOe compared to 1. Despite their general structural and magnetic similarity, 2 and 3 reveal significant differences in magnetic dimensionality: compound 2 exhibits the features of a metamagnet with a threshold field of 1.8 kOe at 4.2 K, while compound 3 resembles a classical magnet with 3D ordering. This difference is discussed in terms of non-stoichiometry of the networks accompanied by the appearance of different numbers of non-magnetic “defects” due to the formation of diamagnetic W(IV) centres.

XAS and XMCD under high magnetic field and low temperature on the energy-dispersive beamline of the ESRF

The present paper demonstrates the feasibility of X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) under high magnetic fields up to 26 T and low temperatures down to 5 K on the ID24 energy-dispersive XAS beamline of the ESRF. The pulsed magnetic field set-up, entirely developed at the ESRF, is described as well as the beamline set-up, the synchronization and the measurement procedure. It allows field strengths up to 30 T. Finally, as an example, we report a recent XMCD study at the Re L2 and L3 absorption edges of the double perovskite Sr2CrReO(6).

Direct evidence for an interdiffused intermediate layer in bi-magnetic core–shell nanoparticles

Core-shell nanoparticles attract continuously growing interest due to their numerous applications, which are driven by the possibility of tuning their functionalities by adjusting structural and morphological parameters. However, despite the critical role interdiffused interfaces may have in the properties, these are usually only estimated in indirect ways. Here we directly evidence the existence of a 1.1 nm thick (Fe,Mn)3O4 interdiffused intermediate shell in nominally γ-Fe2O3-Mn3O4 core-shell nanoparticles using resonant inelastic X-ray scattering spectroscopy combined with magnetic circular dichroism (RIXS-MCD). This recently developed magneto-spectroscopic probe exploits the unique advantages of hard X-rays (i.e., chemical selectivity, bulk sensitivity, and low self-absorption at the K pre-edge) and can be advantageously combined with transmission electron microscopy and electron energy loss spectroscopy to quantitatively elucidate the buried internal structure of complex objects. The detailed information on the structure of the nanoparticles allows understanding the influence of the interface quality on the magnetic properties.

Magnetic manipulation of molecules on a non-magnetic catalytic surface

Non-magnetic Pt catalysts, supported on carbon coated magnetic Co nanoparticles, changed catalytic performance in the presence of an external magnetic field. This behavior relates to an electronic change of Pt induced by a localized magnetic field, which modifies the CO adsorption geometry. In situ resonant inelastic X-ray scattering (RIXS) experiments and theory reveal the change of atop CO adsorption geometry on the Pt catalyst to bridged geometry under an external magnetic field. This observation opens the possibility of catalytic control by means of an external magnetic field.

Evolution of charge and spin state of transition metals in the LaMn1−xCoxO3 perovskite series

Charge and spin state evolution of the transition metals in the LaMn1−xCoxO3 perovskite series was studied by means of high resolution x-ray absorption and emission spectroscopy. The gradual charge transfer from Mn to Co sites was observed upon increasing Co doping. The high spin of the Mn3+∕4+ and Co2+ ions is preserved in the entire solid solution. Co3+ ions reveal low spin state at low doping, while the gradual increase of the average Co3+ spin state is observed at higher cobalt concentrations. The results plausibly explain the observed magnetization anomalies.

Experimental station to study the interaction of intense femtosecond vacuum ultraviolet pulses with matter at TTF1 free electron laser

An experimental station to study the interaction of intense femtosecond vacuum ultraviolet pulses generated by the TTF1 free electron laser (FEL) (DESY, Germany) with solids was developed. The vacuum chamber, the sample holder and the detectors had been designed to fulfill strong constraints caused both by the unique properties of the interacting radiation and by TTF1 FEL innovative design. The applied mounting system allowed one to move and rotate the samples precisely with 4degrees of freedom and to heat them up to the maximal temperature of 1000K. In order to accomplish the in situ growth of thin metallic layers on the sample surfaces, evaporation cells had been installed in the vacuum chamber. A time-of-flight apparatus capable of recording both electrons and ions excited on the solid surfaces by the laser pulses had been included in the chamber design. A pulse energy monitor had been placed in the laser beam outside the experimental chamber. A second energy detector had been mounted inside the chambe...

Toward understanding the chloroquine action at the molecular level in antimalarial therapy--X-ray absorption studies in acetic acid solution.

The local atomic structure around the central iron of the synthetic soluble analog of malarial pigment in acetic acid solution and with addition of chloroquine as found by X-ray absorption spectroscopy is reported. The special interest was drawn to the axial linkage between the central iron atom of the ferriprotoporphyrin IX (FePPIX) coordinated axially to the propionate group of the adjacent FePPIX. This kind of bonding is typical for hematin anhydride. Detailed analysis revealed differences in oxygen coordination sphere (part of dimer linkage bond) between synthetic equivalent of hemozoin in the powder state and dissolved in acetic acid and water at different concentrations mimicking the physiological condition of the parasites food vacuole. The results of performed studies suggest that the molecular structure of synthetic analogue of hemozoin is no longer dimer-like in acidic solution. Further changes in atomic order around Fe are seen after addition of the antimalarial drug chloroquine.