Ultrafast x-ray scattering of xenon nanoparticles: imaging transient states of matter

Femtosecond x-ray laser flashes with power densities of up to 10(14) W/cm(2) at 13.7 nm wavelength were scattered by single xenon clusters in the gas phase. Similar to light scattering from atmospheric microparticles, the x-ray diffraction patterns carry information about the optical constants of the objects. However, the high flux of the x-ray laser induces severe transient changes of the electronic configuration, resulting in a tenfold increase of absorption in the developing nanoplasma. The modification in opaqueness can be correlated to strong atomic charging of the particle leading to excitation of Xe(4+). It is shown that single-shot single-particle scattering on femtosecond time scales yields insight into ultrafast processes in highly excited systems where conventional spectroscopy techniques are inherently blind.     

Evidence for a single hydrogen molecule connected by an atomic chain

Stable, single-molecule conducting-bridge configurations are typically identified from peak structures in a conductance histogram. In previous work on Pt with H2 at cryogenic temperatures it has been shown that a peak near 1G0 identifies a single-molecule Pt-H2-Pt bridge. The histogram shows an additional structure with lower conductance that has not been identified. Here, we show that it is likely due to a hydrogen decorated Pt chain in contact with the H2 molecular bridge.     

Multienergy anomalous diffuse scattering

A new approach to local structure determination is presented. A three-dimensional region of the reciprocal space of a SrTiO(3) single crystal was mapped by measuring x-ray diffuse scattering patterns at different sample orientations in order to reconstruct the local atomic structure. The phase problem was solved by means of anomalous scattering from strontium atoms at photon energies near their K absorption edge. Real-space reconstruction provides the average short-range order atomic arrangement in the vicinity of anomalous scatterers up to a distance of several unit cells.     

Oxidation of Pt(111) under near-ambient conditions

The oxidation of Pt(111) at near-ambient O2 pressures has been followed in situ using x-ray photoelectron spectroscopy (XPS) and ex situ using x-ray absorption spectroscopy (XAS). Polarization-dependent XAS signatures at the O K edge reveal significant temperature- and pressure-dependent changes of the Pt-O interaction. Oxide growth commences via a PtO-like surface oxide that coexists with chemisorbed oxygen, while an ultrathin α-PtO2 trilayer is identified as the precursor to bulk oxidation. These results have important implications for understanding the chemical state of Pt in catalysis.     

Dynamische Theorie der elastischen Elektronenbeugung unter Verwendung komplexer Atomformfaktoren

The two-beam approximation of dynamic electron diffraction in crystals is deduced from successive scattering by two-dimensional gratings. The scattering-amplitude caused by the single grating (phase-grating) is determined by the atomic scattering factors of the single atoms. The use of real atomic scattering factors leads here to the same solutions as the twobeam theory, using the Schroedinger-equation. Anomalous absorptions effects are described in the usual theory by introducing a complex lattice potential into the Schroedinger-equation, taking into account inelastic scattering. A more exact calculation of only elastic scattering by a single atom results in complex atomic scattering factors. Using the complex atomic scattering factors one can describe the anomalous absorption, if recursion-formulae for successive scattering are applied. On the other hand, the transformation to differential equations leads to results, which are not in agreement with experiments. The influence of inelastic scattering for the anomalous absorption can be neglected compared with the complex atomic scattering factors.     

A DFT study of H adsorption on Pt(111) and Pt-Ru(111) surfaces

In this work a comparative analysis between different Pt-Ru(111) surface models and pure Pt(111) surface is presented. Some aspects of the electronic structure of the surfaces and hydrogen adsorption are analysed based on density functional theory calculations. The hydrogen adsorption energy is significantly reduced when Ru is present on the surface. The substitution of Pt atoms by Ru atoms reinforce the Pt-H bond while the metal-metal bond is strongly modified, making the system less stable.     

The utility of resonant soft x-ray scattering and reflectivity for the nanoscale characterization of polymers

The utility of resonant soft x-ray scattering (RSoXS) and reflectivity (RSoXR) is extended and exemplified through the characterization of thin films of polymers relevant to organic solar cells and of dilute polymer solutions. RSoXS and RSoXR are methods that utilize anomalous scattering principles at soft x-ray energies. Soft X-rays cover the carbon, nitrogen and oxygen absorption edges, elements very relevant for polymers and colloids. The rapid changes of optical properties near these absorption edges provide selectivity to specific moieties and high contrast. RSoXR is shown to be a powerful tool for the characterization of bilayers of conducting polymers. The RSoXR results point to an interesting strategy that will allow the chemical interdiffusion and physical roughness at a buried polymer/polymer interface to be determined independently. The high scattering cross sections also allows the investigation of thin films of conjugated polymer blends in transmission at thicknesses for which hard X-rays or neutrons would yield relatively little scattering. By scattering at photon energies that provide strong scattering contrast, even very dilute polymeric solutions yield a useable signal.     

Levitation methods for structural and dynamical studies of liquids at high temperatures

In recent years, levitation methods have been increasingly used to study the atomic structure and dynamics of high-temperature liquids, in particular metallic melts. These methods provide a containerless and, consequently, high-purity sample environment. No corrections for signals due to a crucible need to be made, and deep undercoolings of the liquid become possible, reducing the effect of thermal fluctuations. On the other hand, the sample position and, hence, the scattering geometry is not fixed and the free sample surface exhibits capillary waves. Nevertheless, the combination of levitation techniques with x-ray or neutron sources has proven to be possible and successful. This paper reviews the progress made in this field during the last 10 years or so. It discusses the different levitation techniques: aerodynamic, electromagnetic, electrostatic, as well as the applied spectroscopic techniques: x-ray and neutron diffraction, x-ray absorption and quasi-elastic neutron diffraction. Some recent results are also highlighted.     

Local structure of LiCoO(2) nanoparticles studied by Co K-edge x-ray absorption spectroscopy

We have studied the local structure of LiCoO(2) nanoparticles by Co K-edge x-ray absorption spectroscopy as a function of particle size. Extended x-ray absorption fine structure data reveal substantial changes in the near neighbor distances and the associated mean square relative displacements with decreasing particle size. X-ray absorption near edge structure spectra show clear local geometrical changes with decreasing particle size, similar to those that appear in the charging (delithiation) process. The results suggest that the LiCoO(2) nanoparticles are characterized by a large atomic disorder confined to the Co-O octahedra, similar to the distortions generated during the delithiation, and this disorder should be the primary limiting factor for a reversible diffusion of Li ions when nanoparticles of LiCoO(2) are used as cathode material in rechargeable Li ion batteries.     

X-ray reflectivity data analysis using Bayesian inference: The study of induced Pt magnetization in Pt/Co/Pt

The induced Pt magnetization in a Pt/Co/Pt thin film structure is studied. The normally nonmagnetic Pt acquires a magnetic moment due to the magnetic proximity effect at the Co–Pt interfaces. Element specific Pt structural and magnetic properties are characterized by synchrotron-based resonant x-ray reflectivity and x-ray resonant magnetic reflectivity measurements. An advanced analysis method based on Bayesian inference is used for model fitting of the x-ray data. Using this method, we retrieve the best fit values of material parameters (e.g., thickness, interfacial roughness) from the data. Analysis of x-ray reflectivity data of this specific system shows that the Pt magnetization and Co–Pt interfacial roughness is significantly different between the top and bottom Pt layers, with both values being larger in the top Pt. The successful application of this Bayesian method to study the magnetic and structural properties of a thin film system demonstrates its effectiveness for x-ray reflectivity data analysis.     

Oscillatory magnetic anisotropy in one-dimensional atomic wires

One-dimensional Co atomic wires grown on Pt(997) have been investigated by x-ray magnetic circular dichroism. Strong changes of the magnetic properties are observed as the system evolves from 1D- to 2D-like. The easy axis of magnetization, the magnetic anisotropy energy, and the coercive field oscillate as a function of the transverse width of the wires, in agreement with theoretical predictions for 1D metal systems.     

Initial growth of platinum on oxygen-covered Ni(1 1 0) surfaces

The initial growth of Pt on the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) surfaces has been studied by coaxial impact collision ion scattering spectroscopy (CAICISS), low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Prior to Pt deposition, the atomic structure of the near-surface regions of the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) structures were studied using CAICISS, finding changes to the interlayer spacings due to the adsorption of oxygen. Deposition of Pt on the Ni(1 1 0)-(3 × 1)-O surface led to a random substitutional alloy in the near-surface region at Pt coverages both below and in excess of 1 ML. In contrast, when the surface was treated with 1800 L of atomic oxygen in order to form a NiO(1 1 0) surface, a thin Pt layer was formed upon room temperature Pt deposition. XPS and LEED data are presented throughout to support the CAICISS observations.     

Probing outer-sphere adsorption of aqueous metal complexes at the oxide-water interface with resonant anomalous x-ray reflectivity

Resonant anomalous x-ray reflectivity near the Pt L(III) edge simultaneously revealed the geometric and spectroscopic structures of Pt(NH(3))(4)(2+) ions adsorbed at the quartz(100)-water interface. The derived Pt geometric subprofile shows two discrete "outer-sphere" adsorbed layers, and the interface-specific x-ray absorption edge profile exhibits a significant white-line enhancement compared to the bulk-solution species.     

Enhanced orbital magnetism in Fe(50)Pt(50) nanoparticles

X-ray absorption and magnetic circular dichroism spectra at both the Fe and Pt L(3,2) edges were measured on wet-chemically synthesized monodisperse Fe(50)Pt(50) particles with a mean diameter of 6.3 nm before and after complete removal of the organic ligands and the oxide shell covering the particles by soft hydrogen plasma resulting in a pure metallic state. After thermal treatment of the metallic particles, the coercive field increased by a factor of 6, the orbital magnetic moment at the Fe site increased by 330% and is reduced at the Pt site by 30%, while the effective spin moments did not change. A decrease of the frequency of oscillations in the extended x-ray absorption fine structure at the Pt L(3,2) edges provides evidence for crystallographic changes towards the L1(0) phase.     

Pairing interactions and Gibbs adsorption at the liquid bi-in surface: a resonant X-ray reflectivity study

Resonant x-ray reflectivity measurements from the surface of liquid Bi(22)In(78) find only a modest surface Bi enhancement, with 35 at. % Bi in the first atomic layer. This is in contrast to the Gibbs adsorption in all liquid alloys studied to date, which show surface segregation of a complete monolayer of the low surface tension component. This suggests that surface adsorption in Bi-In is dominated by attractive interactions that increase the number of Bi-In neighbors at the surface. These are the first measurements in which resonant x-ray scattering has been used to quantify compositional changes induced at a liquid alloy surface.     

Special Features of Behavior of Phenomenological Parameters of Thermoelastic Martensitic Transformations in Low-Stability Alloys Based on Titanium Nickelide

The paper presents the results of an analysis of the data on phase and atomic composition changes in the austenite and martensite phases obtained by an in situ x-ray diffraction examination of thermoelastic martensite transitions in the alloys based on titanium nickelide doped with different elements (Fe, Co, Rh, Cu, Pd, Pt, and Au). To this end, the parameters determining the martensitic transformation hysteresis loops were obtained. These were then classified using the x-ray diffraction and phenomenological data.     

First-principles calculations of K-shell x-ray absorption spectra for warm dense ammonia

The x-ray absorption spectroscopy is a powerful tool for the detection of thermodynamic conditions and atomic structures on warm dense matter. Here, we perform first-principles molecular dynamics and x-ray absorption spectrum calculations for warm dense ammonia, which is one of the major constituents of Uranus and Neptune. The nitrogen K-shell x-ray absorption spectrum(XAS) is determined along the Hugoniot curve, and it is found that the XAS is a good indicator of the prevailing thermodynamic conditions. The atomic structures at these conditions are ascertained. Results indicate that the ammonia could dissociate to NH_x(x = 0, 1, or 2) fragments and form nitrogen clusters, and the ratios of these products change with varying conditions. The contributions to the XAS from these products show quite different characteristics,inducing the significant change of XAS along the Hugoniot curve. Further model simulations imply that the distribution of the peak position of atomic XAS is the dominant factor affecting the total XAS.     

Improvement of Nickel-Stanogermanide Contact Properties by Platinum Interlayer

We report an effective method to improve the formation of nickel stanogermanide(Ni Ge Sn) by the incorporation of a platinum(Pt) interlayer. After the Ni/Pt/Ge Sn samples are annealed we obtain uniform Ni Ge Sn thin films,which are characterized by means of sheet resistance, atomic force microscopy, scanning electron microscopy,cross-section transmission electron microscopy, and energy dispersive x-ray spectroscopy. These results show that the presence of Pt increases the smoothness and uniform morphology of Ni Ge Sn films.     

Anomalous dispersion behavior of multiple-wave X-ray diffraction at absorption edges: determination of phase change at resonance

The effects of anomalous dispersion (resonance) on multiple reflection of x rays and their interference in crystals at atomic absorption edges are studied. Intensity ratios of two inversion-symmetry-related multiple diffractions at or near absorption edges exhibit highly phase-sensitive profiles with strong asymmetric characteristics, unlike those far from the edges. A new resonance perturbation Bethe approach is developed to explain this behavior. This leads to direct determination of the phase change for x-ray reflections at resonance.     

Raman effect in the x-ray region

This paper presents a brief review of x-ray Raman scattering and some of our calculations on Raman scattered line shapes from light elements. We summarise the history of the Raman process in the x-ray region and present a detailed theory of the Raman scattering from an atomic many-electron system. Actual calculations of the Raman cross-section using this theory in single-particle approximation are given. The process of internal resonance Raman scattering is also discussed in the same formulation. The Raman cross-section is compared with the cross-sections of other x-ray scattering processes.