X-ray Line Shape Research Articles

Streaked sub-ps-resolution x-ray line shapes and implications for solid-density plasma dynamics (invited).

A high-resolution x-ray spectrometer was coupled with an ultrafast x-ray streak camera to produce time-resolved line shape spectra measured from hot, solid-density plasmas. A Bragg crystal was placed near laser-produced plasma to maximize throughput; alignment tolerances were established by ray tracing. The streak camera produced single-shot, time-resolved spectra, heavily sloped due to photon time-of-flight differences, with sufficient reproducibility to accumulate photon statistics. The images are time-calibrated by the slope of streaked spectra and dewarped to generate spectra emitted at different times defined at the source. The streaked spectra demonstrate the evolution of spectral shoulders and other features on ps timescales, showing the feasibility of plasma parameter measurements on the rapid timescales necessary to study high-energy-density plasmas.

Characterization of the chemical shift and asymmetry indices of praseodium, neodymium, samarium, gadolinium, and terbium compounds by wavelength dispersive X-ray fluorescence (WDXRF)

Emitted X-ray energies, line shapes, fluorescence yields, absorption probabilities and absorption edges of the elements are X-ray fundamental parameters that are of practical significance because they facilitate compositional analysis of complex materials. They are also a potent test of atomic theory. The chemical effects may cause changes in the energy of the X-ray lines and line shapes, such as the full width at half maximum and asymmetry index values depending on the chemical state of the substance. Although these effects vary for each element, the causes of these differences have been investigated. In this study, changes in chemical action values of lanthanide group compounds were investigated using a single crystal wavelength dispersive X-ray spectrometer equipped with a rhodium anode X-ray tube. The Ll and Lη X-ray emission lines are characterized by fitting of the Lorentz function. The chemical shift was investigated according to the chemical bond type, molecular structure, and oxidation number.

Simulation of attosecond transient soft x-ray absorption in solids using generalized Kohn–Sham real-time time-dependent density functional theory

Time-dependent density functional theory (TDDFT) simulations of transient core-level spectroscopies require a balanced treatment of both valence- and core-electron excitations. To this end, tuned range-separated hybrid exchange–correlation functionals within the generalized Kohn–Sham scheme offer a computationally efficient means of simultaneously improving the accuracy of valence and core excitation energies in TDDFT by mitigating delocalization errors across multiple length-scales. In this work range-separated hybrid functionals are employed in conjunction with the velocity-gauge formulation of real-time TDDFT to simulate static as well as transient soft x-ray near-edge absorption spectra in a prototypical solid-state system, monolayer hexagonal boron nitride, where excitonic effects are important. In the static case, computed soft x-ray absorption edge energies and line shapes are seen to be in good agreement with experiment. Following laser excitation by a pump pulse, soft x-ray probe spectra are shown to exhibit characteristic features of population induced bleaching and transient energy shifts of exciton peaks. The methods outlined in this work therefore illustrate a practical means for simulating attosecond time-resolved core-level spectra in solids within a TDDFT framework.

X-ray emission spectroscopy optimization for chemical speciation in laboratory

K X-ray emission spectra emitted from carbon, aluminum, silicon, phosphorus, titanium, chromium, and manganese compounds were measured, using a compact lab-scale flat crystal X-ray fluorescence spectrometer. The sensitivity of K X-ray transitions line-shape, relative to the atom's chemical speciation, is considered. Spectrometer's optimization concerning high energy resolution takes place for each measured fluorescence transition. The detected changes on the measured X-ray line-shapes allow extracting the chemical speciation of the emitting atom. In-lab high-resolution X-ray emission spectroscopy is shown to be a highly versatile technique for materials chemical characterization.

Properties of laser-produced GaAs plasmas measured from highly resolved X-ray line shapes and ratios

The properties of hot, dense plasmas generated by the irradiation of GaAs targets by the Titan laser at Lawrence Livermore National Laboratory were determined by the analysis of high resolution K shell spectra in the 9 keV to 11 keV range. The laser parameters, such as relatively long pulse duration and large focal spot, were chosen to produce a steady-state plasma with minimal edge gradients, and the time-integrated spectra were compared to non-LTE steady state spectrum simulations using the FLYCHK and NOMAD codes. The bulk plasma streaming velocity was measured from the energy shifts of the Ga He-like transitions and Li-like dielectronic satellites. The electron density and the electron energy distribution, both the thermal and the hot non-thermal components, were determined from the spectral line ratios. After accounting for the spectral line broadening contributions, the plasma turbulent motion was measured from the residual line widths. The ionization balance was determined from the ratios of the He-like through F-like spectral features. The detailed comparison of the experimental Ga spectrum and the spectrum simulated by the FLYCHK code indicates two significant discrepancies, the transition energy of a Li-like dielectronic satellite (designated t) and the calculated intensity of a He-like line (x), that should lead to improvements in the kinetics codes used to simulate the X-ray spectra from highly-charged ions.

Development of Thick Electroplated Bismuth Absorbers for Large Collection Area Hard X-ray Transition Edge Sensors

Transition edge sensors (TES) offer some of the highest resolutions for solid-state X-ray spectrometers. We are developing TES detectors for use at hard X-ray synchrotron light sources for energy ranges up to 20 keV. Because TES resolving power scales inversely with the square root of heat capacity, it is important to have an absorber with both a small heat capacity and a large X-ray stopping power. We are developing electroplated bismuth (Bi) absorbers to meet these criteria. Although Bi has a smaller X-ray absorption at 20 keV than gold, the specific heat is up to two orders of magnitude smaller, allowing for much larger collection area (up to 1 mm $^{2}$ ) without significantly increasing the total device specific heat. However, due to its low thermal conductivity, Bi absorbers may have longer thermalization times. Also, some evaporated Bi absorbers may produce spectra with low-energy tails that will hinder X-ray line shape analysis and increase minimum detectability limits of trace metals for X-ray fluorescence microscopy. We examine the impact of plating current density, agitation, film thickness, and seed layer thickness on the grain size, residual resistance ratio, and uniformity of Bi absorbers. Additionally, we discuss processing considerations important for successful electroplating.

Modeling X-ray Line Shapes from Asphaltenes

Structural studies of asphaltene in crude oil have been performed by x-ray diffraction (XRD). The XRD spectra were taken with a Rigaku Dmax 2200V/PC, and built-in Jade™ software was used for initial analysis. XRD was performed with Cu-K-α radiation operating at 40 KV and 40 mA, with a scan rate of 0.001° 2θ per second. The XRD data were first fitted with Pearson VII profiles and then with pseudo-Voigt profiles, and then modeled in Mathematica© using a generalized Fermi function (GFF). These fits also included several different backgrounds (linear, exponential, and Lorentzian). The results are discussed in terms of their accuracy with different combinations of background and line profile.

Pionic hydrogen and friends

Pion-nucleon scattering lengths are directly related to the ground-state level shift and broadening in pionic hydrogen as well as to the pionic deuterium level shift. The level broadening in deuterium measures the strength of pion threshold-production in proton-proton reactions. However, collisional processes during the atomic de-excitation cascade considerably complicate the analysis of X-ray line shapes in order to extract the hadronic broadening. Therefore, additionally the purely electromagnetic twin system muonic hydrogen was studied. Results of these experiments performed at PSI by using a high-resolution crystal spectrometer are discussed in the context with a new analysis approach for the hadronic broadening.

CONSTRAINTS ON POROSITY AND MASS LOSS IN O-STAR WINDS FROM THE MODELING OF X-RAY EMISSION LINE PROFILE SHAPES

We fit X-ray emission line profiles in high resolution XMM-Newton and Chandra grating spectra of the early O supergiant Zeta Pup with models that include the effects of porosity in the stellar wind. We explore the effects of porosity due to both spherical and flattened clumps. We find that porosity models with flattened clumps oriented parallel to the photosphere provide poor fits to observed line shapes. However, porosity models with isotropic clumps can provide acceptable fits to observed line shapes, but only if the porosity effect is moderate. We quantify the degeneracy between porosity effects from isotropic clumps and the mass-loss rate inferred from the X-ray line shapes, and we show that only modest increases in the mass-loss rate (<~ 40%) are allowed if moderate porosity effects (h_infinity <~ R_*) are assumed to be important. Large porosity lengths, and thus strong porosity effects, are ruled out regardless of assumptions about clump shape. Thus, X-ray mass-loss rate estimates are relatively insensitive to both optically thin and optically thick clumping. This supports the use of X-ray spectroscopy as a mass-loss rate calibration for bright, nearby O stars.

K-shell spectroscopy of silicon ions as diagnostic for high electric fields

We developed a detection scheme, capable of measuring X-ray line shape of tracer ions in μm thick layers at the rear side of a target foil irradiated by ultra intense laser pulses. We performed simulations of the effect of strong electric fields on the K-shell emission of silicon and developed a spectrometer dedicated to record this emission. The combination of a cylindrically bent crystal in von Hámos geometry and a CCD camera with its single photon counting capability allows for a high dynamic range of the instrument and background free spectra. This approach will be used in future experiments to study electric fields of the order of TV/m at high density plasmas close to solid density.

Structural origin of gap states in semicrystalline polymers and the implications for charge transport

We quantify the degree of disorder in the {\pi}-{\pi} stacking direction of crystallites of a high performing semicrystalline semiconducting polymer with advanced X-ray lineshape analysis. Using first principles calculations, we obtain the density of states of a system of {\pi}-{\pi} stacked polymer chains with increasing amounts of paracrystalline disorder. We find that for an aligned film of PBTTT the paracrystalline disorder is 7.3%. This type of disorder induces a tail of trap states with a breadth of ~100 meV as determined through calculation. This finding agrees with previous device modeling and provides physical justification for the mobility edge model.

A maximum information utilization approach in X-ray fluorescence analysis

X-ray fluorescence data bases have significant contradictions, and inconsistencies. We have identified that the main source of the contradictions, after the human factors, is rooted in the signal processing approaches. We have developed signal processors to overcome many of the problems by maximizing the information available to the analyst. These non-paralyzable, fully digital signal processors have yielded improved resolution, line shape, tailing and pile up recognition. The signal processors account for and register all events, sorting them into two spectra, one spectrum for the desirable or accepted events, and one spectrum for the rejected events. The information contained in the rejected spectrum is mandatory to have control over the measurement and to make a proper accounting and allocation of the events. It has established the basis for the application of the fundamental parameter method approach. A fundamental parameter program was also developed. The primary X-ray line shape (Lorentzian) is convoluted with a system line shape (Gaussian) and corrected for the sample material absorption, X-ray absorbers and detector efficiency. The peaks also can have, a lower and upper energy side tailing, including the physical interaction based long range functions. It also employs a peak and continuum pile up and can handle layered samples of up to five layers. The application of a fundamental parameter method demands the proper equipment characterization. We have also developed an inverse fundamental parameter method software package for equipment characterisation. The program calculates the excitation function at the sample position and the detector efficiency, supplying an internally consistent system.

Order and strain in main-chain smectic liquid-crystalline polymers and elastomers

The layer correlations in main-chain smectic liquid-crystal polymer and elastomer systems have been studied using high-resolution X-ray scattering. In contrast to side-chain smectic polymers, in main-chain systems the polymer chains are oriented parallel to the layer normal. As a result they couple directly to the lamellar structure and any polymer defect is translated into layer distortions. For the homopolymers the resulting X-ray lineshapes are well described by Lorentzians. This is interpreted as an average of algebraically decaying order in domains with dimensions of hundreds of nm and a wide dispersion of sizes. The elastomers show much broader peaks than the correponding polymers. This is attributed to strong non-uniform strain within the finite-size domains due to defects of the layer structure.

Main-chain smectic liquid-crystalline polymers as randomly disordered systems

We report a high-resolution X-ray lineshape study of main-chain smectic polymers. The results indicate that the layer ordering differs fundamentally from the algebraic decay typical for other smectic liquid-crystalline systems. The lineshapes are best described by broad squared Lorentzians indicating some form of short-range correlations. However, several higher harmonics are observed, which excludes simple liquid-like short-range order. This behaviour is tentatively attributed to a random field of defects associated with entangled hairpins in the main-chain polymer structure.

Lamellar Gels and Spontaneous Vesicles in Catanionic Surfactant Mixtures

Caillé analysis of the small-angle X-ray line shape of the lamellar phase of 7:3 wt/wt cetyltrimethylammonium tosylate (CTAT)/sodium dodecylbenzene sulfonate (SDBS) bilayers shows that the bending elastic constant is kappa = (0.62 +/- 0.09)k(B)T. From this and previous results, the Gaussian curvature constant is kappa = (-0.9 +/- 0.2)k(B)T. For 13:7 wt/wt CTAT/SDBS bilayers, the measured bending elasticity decreases with increasing water dilution, in good agreement with predictions based on renormalization theory, giving kappa(o) = 0.28k(B)T. These results show that surfactant mixing is sufficient to make kappa approximately k(B)T, which promotes strong, Helfrich-type repulsion between bilayers that can dominate the van der Waals attraction. These are necessary conditions for spontaneous vesicles to be equilibrium structures. The measurements of the bending elasticity are confirmed by the transition of the lamellar phase of CTAT/SDBS from a turbid, viscoelastic gel to a translucent fluid as the water fraction is decreased below 40 wt %. Freeze-fracture electron microscopy shows that the gel is characterized by spherulite defects made possible by spontaneous bilayer curvature and low bending elasticity. This lamellar gel phase is common to a number of catanionic surfactant mixtures, suggesting that low bending elasticity and spontaneous curvature are typical of these mixtures that form spontaneous vesicles.

RETRACTED: Flexible bilayers with spontaneous curvature lead to lamellar gels and spontaneous vesicles

Mixtures of cetyltrimethylammonium tosylate (CTAT) and sodium dodecylbenzene sulfonate (SDBS) in water form a fluid lamellar phase at < or = 40 wt % water but surprisingly turn into viscous gels at higher water fractions. The gels are characterized by spherulite and other bilayer defects consistent with a low bending elasticity, kappa approximately k(B)T, and a nonzero spontaneous curvature. Caillé analysis of the small-angle x-ray line shape confirms that for 7:3 wt:wt CTAT:SDBS bilayers at 50% water, kappa = 0.62 +/- 0.09 k(B)T and kappa = -0.9 +/- 0.2 k(B)T. For 13:7 wt:wt CTAT:SDBS bilayers, the measured bending elasticity decreases with increasing water dilution in good agreement with predictions based on renormalization theory, giving kappa(o) = 0.28 k(B)T. These results show that surfactant mixing is sufficient to make kappa approximately k(B)T, which promotes strong, Helfrich-type repulsion between bilayers that can dominate the van der Waals attraction. These are necessary conditions for spontaneous vesicles formed at even higher water fractions to be equilibrium structures.

X-ray line shapes of metals: Exact solutions of a final-state interaction model

By means of model calculations for an independent-electron metal, we obtain exact line shapes for the photon absorption, emission, and photoemission spectra of core states, including electronic relaxation. In all cases we find an x-ray edge anomaly. For the absorption and emission spectra this anomaly is superposed on a continuum resembling Elliott exciton theory. We display how the spectra evolve from the exciton limit to the free-electron limit as the final-state interaction strength is decreased or the Fermi energy increased. We compare the spectra obtained for different final-state interactions and find that different types of interactions produce different spectral shapes. Away from threshold the absorption and emission profiles show an enhancement of the free-electron result, as predicted by the screened-exciton theory. Our results offer potential explanations for (i) incompatibilities between threshold exponents and exponents extracted from other data, (ii) the occurrence of nearly symmetric x-ray photoemission lines, and (iii) the lack of mirror symmetry of absorption and emission edges.

Ferritic Fine Structure Characteristics in Hot Die Forged Powder Steels. I. Effect of Heating Temperature during Die Forging on Ferritic Fine Structure in Specimens of Powder Technical Grade Iron and Carbon Steels

We have studied the effect of the composition and heating temperature during die forging on the microstructure and fine structure of ferrite in powder iron and powder carbon steels. From the structural characteristics obtained for different planes of the blank, we used harmonic analysis of the x-ray line shape to establish the nonuniformity of deformation over the volume. We have established the heating temperature during die forging of powder technical grade iron and carbon steels, for which the deformation is close to uniform over the die forging volume: 1050 °C for technical grade iron and low-carbon steel, 1100 °C for carbon steel.

Multiple Grains in Nanocrystals: Effect of Initial Shape and Size on Transformed Structures Under Pressure

Pressure-induced structural transformations in spherical and faceted gallium arsenide nanocrystals of various shapes and sizes are investigated with a parallel molecular-dynamics approach. The results show that the pressure for zinc blende to rocksalt structural transformation depends on the nanocrystal size, and all nanocrystals undergo nonuniform deformation during the transformation. Spherical nanocrystals above a critical diameter >/=44 A transform with grain boundaries. Faceted nanocrystals of comparable size have grain boundaries in 60% of the cases, whereas the other 40% are free of grain boundaries. The structure of transformed nanocrystals shows that domain orientation and strain relative to the initial zinc blende lattice are not equivalent. These observations may have implications in interpreting the experimental x-ray line shapes from transformed nanocrystals.

Preparation and characterisation of Pt–Ru model electrodes for the direct methanol fuel cell

Pt–Ru alloys for the direct methanol fuel cell (DMFC) with Ru contents between 10 and 60 at.% were synthesised in two ways: on the one hand, polycrystalline Pt–Ru reference samples were prepared by arc melting starting from appropriate mixtures of Pt and Ru powders. On the other hand, nanocrystalline Pt–Ru particles of about 8 nm were electrochemically deposited in carbon/Nafion™ layers on glassy carbon discs for electrochemical measurements. The structural properties of the Pt–Ru model electrodes, such as lattice constant, grain size and alloy composition, were investigated by X-ray line shape analysis and scanning electron microscopy (EDX). Analysing the continuous peak shift of the Pt Bragg reflexes with increasing Ru content, we established a calibration curve for Pt–Ru alloys which allows to determine the Ru content of samples with unknown composition by simple XRD measurements. The Pt–Ru samples were electrochemically characterised recording quasi-stationary current–potential curves with regard to the influence of the Pt–Ru composition on the methanol oxidation. The Pt–Ru catalyst with 50 at.% Ru turned out to be most active for the methanol electrooxidation.