Photon-in/photon-out spectroscopy at the I20-scanning beamline at diamond light source.

A scanning multi-crystal x-ray emission spectrometer to perform photon-in/photon-out spectroscopy at the I20-Scanning beamline at Diamond Light Source is described. The instrument, equipped with three analyzer crystals, is based on a 1 m Rowland circle spectrometer operating in the vertical plane. The energy resolution of the spectrometer is of the order of 1 eV, having sufficient resolving power to overcome the core-hole lifetime broadening of most of the transition metals-edges.

EXAFS and XANES analysis of oxides at the nanoscale.

Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.

X-ray absorption study of the local structure at the NiO/oxide interfaces.

This work reports an X-ray absorption near-edge structure (XANES) spectroscopy study at the Ni K-edge in the early stages of growth of NiO on non-ordered SiO2, Al2O3 and MgO thin films substrates. Two different coverages of NiO on the substrates have been studied. The analysis of the XANES region shows that for high coverages (80 Eq-ML) the spectra are similar to that of bulk NiO, being identical for all substrates.

Colored and transparent oxide thin films prepared by magnetron sputtering: the glass blower approach.

This work describes the reactive magnetron sputtering processing at room temperature of several mixed oxide MxSiyOz thin films (M: Fe, Ni, Co, Mo, W, Cu) intended for optical, coloring, and aesthetic applications. Specific colors can be selected by adjusting the plasma gas composition and the Si-M ratio in the magnetron target. The microstructure and chemistry of the films are characterized by a large variety of techniques including X-ray photoemission spectroscopy, X-ray absorption spectroscopy (XAS), and infrared spectroscopy, while their optical properties are characterized by UV-vis transmission and reflection analysis.

Ab initio X-ray absorption spectroscopy study of the solvation structure of Th(IV), U(IV), and Np(IV) in aqueous solution.

The coordination structures of U(IV), Np(IV), and Th(IV) in aqueous solution have been determined by studying the X-ray absorption near edge structure (XANES) of the actinide (An) L(3)-edge absorption spectra. The high sensitivity of XANES to the bonding geometry provides an unambiguous determination of the coordination polyhedron. On the basis of the comparison of ab initio computations with the experimental data we conclude that the hydration sphere of the three An(IV) aqua-ions studied is best modeled by 9 water molecules forming a tricapped trigonal prism.

How the local geometry of the Cu-binding site determines the thermal stability of blue copper proteins.

Identifying the factors that govern the thermal resistance of cupredoxins is essential for understanding their folding and stability, and for improving our ability to design highly stable enzymes with potential biotechnological applications. Here, we show that the thermal unfolding of plastocyanins from two cyanobacteria--the mesophilic Synechocystis and the thermophilic Phormidium--is closely related to the short-range structure around the copper center. Cu K-edge X-ray absorption spectroscopy shows that the bond length between Cu and the S atom from the cysteine ligand is a key structural factor that correlates with the thermal stability of the cupredoxins in both oxidized and reduced states.

Co nanoparticles inserted into a porous carbon amorphous matrix: the role of cooling field and temperature on the exchange bias effect.

We report unusual cooling field dependence of the exchange bias in oxide-coated cobalt nanoparticles embedded within the nanopores of a carbon matrix. The size-distribution of the nanoparticles and the exchange bias coupling observed up to about 200 K between the Co-oxide shell (∼3-4 nm) and the ferromagnetic Co-cores (∼4-6 nm) are the key to understand the magnetic properties of this system. The estimated values of the effective anisotropy constant and saturation magnetization obtained from the fit of the zero-field cooling and field cooling magnetization vs.

Relationship between the structural distortion and the Mn electronic state in La1-xCaxMnO3: a Mn K-edge XANES study.

A theoretical study of the X-ray absorption near-edge structure (XANES) spectra at the Mn K-edge in the La(1-x)Ca(x)MnO(3) series is reported. The relationship between the edge shift, the Ca-La substitution and the distortion of the MnO(6) octahedra in these systems has been studied. It is shown that, by correctly considering these effects simultaneously, the experimental XANES data are consistent with the presence of two different Mn local environments in the intermediate La(1-x)Ca(x)MnO(3) compounds.

Origin of the X-ray magnetic circular dichroism at the L-edges of the rare-earths in RxR(1-x)'Al2 systems.

An X-ray magnetic circular dichroism (XMCD) study performed at the rare-earth L(2,3)-edges in the R(x)R(1-x)'Al(2) compounds is presented. It is shown that both R and R' atoms contribute to the XMCD recorded at the L-edges of the selected rare-earth, either R or R'. The amplitude of the XMCD signal is not directly correlated to the magnetization or to the value of the individual (R, R') magnetic moments, but it is related to the molecular field acting on the rare-earth tuned in the photoabsorption process.

Ab initio X-ray absorption spectroscopy study of the solvation structure of yttrium (III) in dimethyl sulfoxide.

The solvation structure of yttrium (III) in dimethyl sulfoxide has been determined by studying both the extended X-ray absorption fine structure (EXAFS) and the X-ray absorption near edge structure (XANES) regions of the Y K-edge absorption spectra. Although the EXAFS technique provides accurate information about the next neighbors coordination distances, no unambiguous determination of the coordination polyhedron is obtained. This failure is counteracted by the study of the near-edge part of the absorption spectrum (XANES) because of its high sensitivity to the bonding geometry.

Temperature dependence of the Ho L2-edge XMCD spectra of Ho6Fe23.

An X-ray magnetic circular dichroism (XMCD) study performed at the Ho L2,3-edges in Ho6Fe23 as a function of temperature is presented. It is demonstrated that the anomalous temperature dependence of the Ho L2-edge XMCD signal is due to the magnetic contribution of Fe atoms. By contrast, the Ho L3-edge XMCD directly reflects the temperature dependence of the Ho magnetic moment.

Disentanglement of magnetic contributions in multi-component systems by using X-ray magnetic circular dichroism at a single absorption edge.

X-ray magnetic circular dichroism (XMCD) has become in recent years an outstanding tool for studying magnetism. Its element specificity, inherent to core-level spectroscopy, combined with the application of magneto-optical sum rules allows quantitative magnetic measurements at the atomic level. These capabilities are now incorporated as a standard tool for studying the localized magnetism in many systems.

The interplay of the 3d9 and 3d10L electronic configurations in the copper K-edge XANES spectra of Cu(II) compounds.

A theoretical analysis of the X-ray absorption near-edge structure spectra at the Cu K-edge in several divalent copper [Cu(II)] compounds showing a distorted nearest-neighborhood around copper is presented. The experimental spectra of CuO and KCuF(3) have been compared with computations performed in the framework of the multiple-scattering theory. The results show that ab initio single-channel multiple-scattering calculations are not able to reproduce the experimental spectra.

The hydration of Cu2+: Can the Jahn-Teller effect be detected in liquid solution?

The long elusive structure of Cu(II) hydrate in aqueous solutions, classically described as a Jahn-Teller distorted octahedron and recently proposed to be a fivefold coordination structure [Pasquarello et al., Science 291, 856 (2001)], has been probed with x-ray-absorption spectroscopy by performing a combined theoretical and experimental analysis. Two absorption channels were needed to obtain a proper reproduction of the x-ray-absorption near-edge structure (XANES) region spectrum, as already observed in other Cu(II) complexes [Chaboy et al.

Nature of metal binding sites in Cu(II) complexes with histidine and related N-coordinating ligands, as studied by EXAFS.

Knowledge of the complexes formed by N-coordinating ligands and Cu(II) ions is of relevance in understanding the interactions of this ion with biomolecules. Within this framework, we investigated Cu(II) complexation with mono- and polydentate ligands, such as ammonia, ethylenediamine (en), and phthalocyanine (Pc). The obtained Cu-N coordination distances were 2.