Search

Abstract This study probes the electrochemical intercalation mechanism of Li into graphitic carbon using x-ray Raman spectroscopy (XRS), an inelastic x-ray scattering technique. Operando and high resolution spectra of electrochemically lithiated composite graphitic electrodes at discrete states of Li uptake (stages III, II and I) show gradually changing spectral features with Li intercalation, the end state agreeing well with chemically fully lithiated LiC 6 highly oriented pyrolytic graphite (HOPG). The two most dominant changes in the XRS spectrum of the C-K edge are the reduced intensity of the π* peak and shift the onset of the σ* states to lower energies upon full lithiation. The excellent instrumental energy resolution uncovered novel spectral features and, thus, electronic changes with varying lithium content. The general spectral changes with progressing Li intercalation agree well with our accompanying DFT calculations. [ABSTRACT FROM AUTHOR]

We report high-energy-resolution X-ray absorption spectroscopy detection of ethylene and CO ligands adsorbed on catalytically active iridium centers isolated on zeolite HY and on MgO supports. The data are supported by density functional theory and FEFF X-ray absorption near-edge modelling, together with infrared (IR) spectra. The results demonstrate that high-energy-resolution X-ray absorption spectra near the iridium LIII (2p3/2) edge provide clearly ascribable, distinctive signatures of the ethylene and CO ligands and illustrate effects of supports and other ligands. This X-ray absorption technique is markedly more sensitive than conventional IR spectroscopy for characterizing surface intermediates, and it is applicable to samples having low metal loadings and in reactive atmospheres and is expected to have an increasing role in catalysis research by facilitating the determination of mechanisms of solid-catalyzed reactions through identification of reaction intermediates in working catalysts. [ABSTRACT FROM AUTHOR]

Photocatalysis is a promising concept for the direct conversion of solar energy into fuels and chemicals. The design, experimental protocol, and performance of a multimodal and versatile flow reactor for the characterization of powdered and immobilized photocatalysts are herein presented. Ultimately, this instrument enables rigorous evaluation of photocatalysis performance metrics. The apparatus quantifies transient gas-phase reaction products via online real-time gas analyzer mass spectrometry (RTGA-MS). For H2, the most challenging gas, the photocatalytic system's RTGA-MS gas detection sensitivity spans over three orders of magnitude and can detect down to tens of parts per million under atmospheric conditions. Using Pt nanoparticles supported on anatase TiO2 photocatalyst via wet impregnation, the instrument's capability for the characterization of photocatalytic H2 evolution is demonstrated, resulting in an apparent quantum yield (AQY) of 48.1% ± 0.9% at 320 nm, 45.7% ± 0.3% at 340 nm and 31% ± 1% at 360 nm. The photodeposition of Pt on anatase TiO2 was employed to demonstrate the instrument's capability to track the transient behavior of photocatalysts, resulting in an improved 55% ± 2% AQY for H2 evolution at 340 nm from aqueous methanol. This photocatalytic instrument enables systematic study of a wide variety of photocatalytic reactions such as water splitting and CO2 reduction to valuable C2+ fuels and chemicals. [ABSTRACT FROM AUTHOR]

X-ray free-electron lasers (FELs) have opened unprecedented possibilities to study the structure and dynamics of matter at an atomic level and ultra-fast timescale. Many of the techniques routinely used at storage ring facilities are being adapted for experiments conducted at FELs. In order to take full advantage of these new sources several challenges have to be overcome. They are related to the very different source characteristics and its resulting impact on sample delivery, X-ray optics, X-ray detection and data acquisition. Here it is described how photon-in photon-out hard X-ray spectroscopy techniques can be applied to study the electronic structure and its dynamics of transition metal systems with ultra-bright and ultra-short FEL X-ray pulses. In particular, some of the experimental details that are different compared with synchrotron-based setups are discussed and illustrated by recent measurements performed at the Linac Coherent Light Source. [ABSTRACT FROM AUTHOR]

Abstract: At the 5.5MV Tandem VdG accelerator of the Institute of Nuclear Physics of N.C.S.R. “Demokritos”, Athens, Greece, an external ion-beam set-up has been recently developed and installed. The aim of this development was to integrate the analytical capabilities of the PIXE, RBS and PIGE ion beam techniques in one experimental set-up, so that to attain a complete elemental and near surface structural characterization of samples in an almost non-destructive way and without any limitation concerning their size or conductive state. A careful 3D mechanical drawing optimized the set-up experimental parameters achieving probe dimensions at the millimeter range (1mm2) and fulfilling the special requirements imposed for optimum performance of the aforementioned techniques, including the possibility to use heavier, than protons, ion beams. For the digital pulse processing of the X-ray, γ-ray and charged particle detector signals, novel hardware and software tools were developed based on a custom FPGA configuration. The first applications were focused in the quality control of materials that have been intentionally contaminated with a particular tracer-element (“tagged” materials). The tagged materials which were developed and tested are technologically authentic replicas of ancient attic ceramics with black glazed decoration. Analytical diagnostic studies were carried out for a few representative paintings of contemporary Greek painters in order to identify and document materials/pigments and techniques and eventually to prevent trade of fakes. Finally, ancient glass beads were also examined with respect to the sodium concentration and its in-depth homogeneity. [Copyright &y& Elsevier]

In the present work, the influence of the secondary fluorescence enhancement in confocal X-ray microscopy analysis is studied when stratified type of materials are examined. Through a proper mathematical formalism, an exact global theoretical model is presented which accounts for the secondary fluorescence enhancement when either particle (3D-Micro particle induced X-ray emission) or photon (3D-Micro X-ray fluorescence) microbeams are used in the excitation channel. The contribution of the secondary fluorescence effect to the confocal X-ray intensity profiles was calculated for some typical representative cases. In addition, the influence of several experimental parameters was examined in terms of their influence in the absolute intensity and shape of the secondary fluorescence intensity profile. [ABSTRACT FROM AUTHOR]

This paper provides a review of the characterization of organic systems via X‑ray Raman scattering (XRS) and a step-by-step guidance for its application. We present the fundamentals of XRS required to use the technique and discuss the main parameters of the experimental set-ups to optimize spectral and spatial resolution while maximizing signal-to-background ratio. We review applications that target the analysis of mixtures of organic compounds, the identification of minor spectral features, and the spatial discrimination in heterogeneous systems. We discuss the recent development of the direct tomography technique, which utilizes the XRS process as a contrast mechanism for assessing the three-dimensional spatially resolved carbon chemistry of complex organic materials. We conclude by exposing the current limitations and provide an outlook on how to overcome some of the existing challenges and advance future developments and applications of this powerful technique for complex organic systems. [ABSTRACT FROM AUTHOR]

The ability to study chemical dynamics on ultrafast timescales has greatly advanced with the introduction of X-ray free electron lasers (XFELs) providing short pulses of intense X-rays tailored to probe atomic structure and electronic configuration. Fully exploiting the full potential of XFELs requires specialized experimental endstations along with the development of techniques and methods to successfully carry out experiments. The liquid jet endstation (LJE) at the Linac Coherent Light Source (LCLS) has been developed to study photochemistry and biochemistry in solution systems using a combination of X-ray solution scattering (XSS), X-ray absorption spectroscopy (XAS), and X-ray emission spectroscopy (XES). The pump–probe setup utilizes an optical laser to excite the sample, which is subsequently probed by a hard X-ray pulse to resolve structural and electronic dynamics at their intrinsic femtosecond timescales. The LJE ensures reliable sample delivery to the X-ray interaction point via various liquid jets, enabling rapid replenishment of thin samples with millimolar concentrations and low sample volumes at the 120 Hz repetition rate of the LCLS beam. This paper provides a detailed description of the LJE design and of the techniques it enables, with an emphasis on the diagnostics required for real-time monitoring of the liquid jet and on the spatiotemporal overlap methods used to optimize the signal. Additionally, various scientific examples are discussed, highlighting the versatility of the LJE. [ABSTRACT FROM AUTHOR]

We report the time-resolved femtosecond evolution of the K-shell X-ray emission spectra of iron during high intensity illumination of X-rays in a micron-sized focused hard X-ray free electron laser (XFEL) beam. Detailed pulse length dependent measurements revealed that rapid spectral energy shift and broadening started within the first 10 fs of the X-ray illumination at intensity levels between 1017 and 1018 W cm-2. We attribute these spectral changes to the rapid evolution of high-density photoelectron mediated secondary collisional ionization processes upon the absorption of the incident XFEL radiation. These fast electronic processes, occurring at timescales well within the typical XFEL pulse durations (i.e., tens of fs), set the boundary conditions of the pulse intensity and sample parameters where the widely-accepted 'probe-before-destroy' measurement strategy can be adopted for electronic-structure related XFEL experiments. [ABSTRACT FROM AUTHOR]

Supercritical fluids (SCFs) can be found in a variety of environmental and industrial processes. They exhibit an anomalous thermodynamic behavior, which originates from their fluctuating heterogeneous micro-structure. Characterizing the dynamics of these fluids at high temperature and high pressure with nanometer spatial and picosecond temporal resolution has been very challenging. The advent of hard x-ray free electron lasers has enabled the development of novel multi-pulse ultrafast x-ray scattering techniques, such as x-ray photon correlation spectroscopy (XPCS) and x-ray pump x-ray probe (XPXP). These techniques offer new opportunities for resolving the ultrafast microscopic behavior in SCFs at unprecedented spatiotemporal resolution, unraveling the dynamics of their micro-structure. However, harnessing these capabilities requires a bespoke high-pressure and high-temperature sample system that is optimized to maximize signal intensity and address instrument-specific challenges, such as drift in beamline components, x-ray scattering background, and multi-x-ray-beam overlap. We present a pressure cell compatible with a wide range of SCFs with built-in optical access for XPCS and XPXP and discuss critical aspects of the pressure cell design, with a particular focus on the design optimization for XPCS. [ABSTRACT FROM AUTHOR]

High‐energy‐resolution fluorescence detection (HERFD) X‐ray absorption spectroscopy at SSRL is combined with density functional theory and FEFF simulations ascribing spectral features to ethylene and CO ligands adsorbed on catalytically active iridium centers isolated on zeolite HY and on MgO, pushing detection limits below those of conventional infrared spectroscopy, and allowing XAS to identify reactionary intermediates. More information can be found in the Full Paper by D. A. Dixon, S. R. Bare, B. C. Gates et al. on page 14760. [ABSTRACT FROM AUTHOR]

Invited for the cover of this issue are the groups of David A. Dixon at the University of Alabama, Simon R. Bare at Stanford Synchrotron Radiation Lightsource and Bruce C. Gates at the University of California, Davis. The image depicts a visual representation of the key conclusion of the work. Read the full text of the article at . [ABSTRACT FROM AUTHOR]

Valence-to-core x-ray emission spectroscopy (VtC XES) combines the sample flexibility and element specificity of hard x-rays with the chemical environment sensitivity of valence spectroscopy. We extend this technique to study geometric and electronic structural changes induced by photoexcitation in the femtosecond time domain via laser-pump, x-ray probe experiments using an x-ray free electron laser. The results of time-resolved VtC XES on a series of ferrous complexes [Fe(CN)2n(2, 2′-bipyridine)3−n]−2n+2, n = 1, 2, 3, are presented. Comparisons of spectra obtained from ground state density functional theory calculations reveal signatures of excited state bond length and oxidation state changes. An oxidation state change associated with a metal-to-ligand charge transfer state with a lifetime of less than 100 fs is observed, as well as bond length changes associated with metal-centered excited states with lifetimes of 13 ps and 250 ps. [ABSTRACT FROM AUTHOR]

The electrochemical splitting of water holds great potential as a method for producing clean fuels by storing electricity from intermittent energy sources. The efficiency of such a process would be greatly facilitated by incorporating more active catalysts based on abundant materials for the oxygen evolution reaction. Manganese oxides are promising as catalysts for this reaction. Recent reports show that their activity can be drastically enhanced when modified with gold. Herein, we investigate highly active mixed Au-MnO x thin films for the oxygen evolution reaction, which exhibit more than five times improvement over pure MnO x . These films are characterized with operando X-ray Absorption Spectroscopy, which reveal that Mn assumes a higher oxidation state under reaction conditions when Au is present. The magnitude of the enhancement is correlated to the size of the Au domains, where larger domains are the more beneficial. [ABSTRACT FROM AUTHOR]

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effects of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide. [ABSTRACT FROM AUTHOR]

We investigate the sensitivity and potential of a synergistic experiment-theory X-ray Raman spectroscopy (XRS) methodology on revealing and following the static and dynamic electronic structure of high explosive molecular materials. We show that advanced ab-initio theoretical calculations accounting for the core-hole effect based on the Bethe-Salpeter Equation (BSE) approximation are critical for accurately predicting the shape and the energy position of the spectral features of C and N core-level spectra. Moreover, the incident X-ray dose typical XRS experiments require can induce, in certain unstable structures, a prominent radiation damage at room temperature. Upon developing a compatible cryostat module for enabling cryogenic temperatures (≈ 10 K) we suppress the radiation damage and enable the acquisition of reliable experimental spectra in excellent agreement with the theory. Overall, we demonstrate the high sensitivity of the recently available state-of-the-art X-ray Raman spectroscopy capabilities in characterizing the electronic structure of high explosives. At the same time, the high accuracy of the theoretical approach may enable reliable identification of intermediate structures upon rapid chemical decomposition during detonation. Considering the increasing availability of X-ray free-electron lasers, such a combined experiment-theory approach paves the way for time-resolved dynamic studies of high explosives under detonation conditions. [ABSTRACT FROM AUTHOR]

Here, we describe a new synchrotron X-ray Fluorescence (XRF) imaging instrument with an integrated High Energy Fluorescence Detection X-ray Absorption Spectroscopy (HERFD-XAS) spectrometer at the Stanford Synchrotron Radiation Lightsource at beamline 6-2. The X-ray beam size on the sample can be defined via a range of pinhole apertures or focusing optics. XRF imaging is performed using a continuous rapid scan system with sample stages covering a travel range of 250 × 200 mm2, allowing for multiple samples and/or large samples to be mounted. The HERFD spectrometer is a Johann-type with seven spherically bent 100 mm diameter crystals arranged on intersecting Rowland circles of 1 m diameter with a total solid angle of about 0.44% of 4π sr. A wide range of emission lines can be studied with the available Bragg angle range of ∼64.5°–82.6°. With this instrument, elements in a sample can be rapidly mapped via XRF and then selected features targeted for HERFD-XAS analysis. Furthermore, utilizing the higher spectral resolution of HERFD for XRF imaging provides better separation of interfering emission lines, and it can be used to select a much narrower emission bandwidth, resulting in increased image contrast for imaging specific element species, i.e., sparse excitation energy XAS imaging. This combination of features and characteristics provides a highly adaptable and valuable tool in the study of a wide range of materials. [ABSTRACT FROM AUTHOR]

We present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100-2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique ability to characterize frozen solutions of radiation- and temperature-sensitive samples. [ABSTRACT FROM AUTHOR]

Coherent nonlinear spectroscopies and imaging in the X-ray domain provide direct insight into the coupled motions of electrons and nuclei with resolution on the electronic length scale and timescale. The experimental realization of such techniques will strongly benefit from access to intense, coherent pairs of femtosecond X-ray pulses. We have observed phase-stable X-ray pulse pairs containing more than 3 × 107 photons at 5.9 keV (2.1 Å) with ∼1 fs duration and 2 to 5 fs separation. The highly directional pulse pairs are manifested by interference fringes in the superfluorescent and seeded stimulated manganese Kα emission induced by an X-ray free-electron laser. The fringes constitute the time-frequency X-ray analog of Young’s double-slit interference, allowing for frequency domain X-ray measurements with attosecond time resolution. [ABSTRACT FROM AUTHOR]

Meteor impacts can induce unique pressure‐dependent structural changes in minerals due to the propagation of shock waves. Plagioclase—ubiquitous throughout the Earth's crust, extraterrestrial bodies, and meteorites—is commonly used for reconstructing the impact history and conditions of the parent bodies. However, there have been unresolved inconsistencies in the interpretation of shock transformations across previous studies: The pressure at which amorphization begins and the process by which it occurs is the subject of ongoing debate. Here, we utilize time‐resolved in situ X‐ray diffraction (XRD) to probe the phase transformation pathway of plagioclase during shock compression at a sub‐nanosecond timescale. Direct amorphization begins at pressures much lower than what was previously assumed, just above the Hugoniot elastic limit of 5 GPa, with full amorphization to a high‐density amorphous phase, observed at 32(10) GPa and 20 ns. Upon release, the material partially recrystallizes back into the original structure, demonstrating a memory effect. [ABSTRACT FROM AUTHOR]

Determination of electronic structures during chemical reactions remains challenging in studies which involve reactions in the millisecond timescale, toxic chemicals, and/or anaerobic conditions. In this study, a three‐dimensionally (3D) microfabricated microfluidic mixer platform that is compatible with time‐resolved X‐ray absorption and emission spectroscopy (XAS and XES, respectively) is presented. This platform, to initiate reactions and study their progression, mixes a high flow rate (0.50–1.5 ml min−1) sheath stream with a low‐flow‐rate (5–90 µl min−1) sample stream within a monolithic fused silica chip. The chip geometry enables hydrodynamic focusing of the sample stream in 3D and sample widths as small as 5 µm. The chip is also connected to a polyimide capillary downstream to enable sample stream deceleration, expansion, and X‐ray detection. In this capillary, sample widths of 50 µm are demonstrated. Further, convection–diffusion‐reaction models of the mixer are presented. The models are experimentally validated using confocal epifluorescence microscopy and XAS/XES measurements of a ferricyanide and ascorbic acid reaction. The models additionally enable prediction of the residence time and residence time uncertainty of reactive species as well as mixing times. Residence times (from initiation of mixing to the point of X‐ray detection) during sample stream expansion as small as 2.1 ± 0.3 ms are also demonstrated. Importantly, an exploration of the mixer operational space reveals a theoretical minimum mixing time of 0.91 ms. The proposed platform is applicable to the determination of the electronic structure of conventionally inaccessible reaction intermediates. [ABSTRACT FROM AUTHOR]

Monolayer MoS2 is a promising semiconductor to overcome the physical dimension limits of microelectronic devices. Understanding the thermochemical stability of MoS2 is essential since these devices generate heat and are susceptible to oxidative environments. Herein, the promoting effect of molybdenum oxides (MoOx) particles on the thermal oxidation of MoS2 monolayers is shown by employing operando X‐ray absorption spectroscopy, ex situ scanning electron microscopy and X‐ray photoelectron spectroscopy. The study demonstrates that chemical vapor deposition‐grown MoS2 monolayers contain intrinsic MoOx and are quickly oxidized at 100 °C (3 vol% O2/He), in contrast to previously reported oxidation thresholds (e.g., 250 °C, t ≤ 1 h in the air). Otherwise, removing MoOx increases the thermal oxidation onset temperature of monolayer MoS2 to 300 °C. These results indicate that MoOx promote oxidation. An oxide‐free lattice is critical to the long‐term stability of monolayer MoS2 in state‐of‐the‐art 2D electronic, optical, and catalytic applications. [ABSTRACT FROM AUTHOR]

We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N, and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excitedstate electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions. [ABSTRACT FROM AUTHOR]

• An air exposed Ni 5 Ga 3 catalyst was investigated for CO 2 hydrogenation to methanol. • Upon air exposure a surface Ga oxide shell forms. • In-situ studies reveal complete reduction of the Ga oxide only at high temperatures. • The surface oxidized Ni 5 Ga 3 is more active compared to a fully reduced Ni 5 Ga 3 catalyst. • Surface amorphous Ga 2 O 3 promotes methanol synthesis. A δ -Ni 5 Ga 3 /SiO 2 catalyst, which is highly active and stable for thermal CO 2 hydrogenation to methanol, was investigated to understand its surface dynamics during reaction conditions. The catalyst was prepared, tested and characterized using a multitude of techniques, including ex-situ XRD (X-ray Diffraction), TEM (Transmission Electron Microscopy), H 2 -TPR (Temperature Programmed Reduction), CO chemisorption, along with in-situ ETEM (Environmental Transmission Electron Microscopy), APXPS (Ambient Pressure X-ray Photoelectron Spectroscopy) and HERFD-XAS (High Energy Resolution Fluorescence Detected X-Ray Absorption Spectroscopy). Upon air exposure Ga migrates from the subsurface region to the surface of the nanoparticles forming a Ga-oxide shell surrounding a metallic core. The oxide shell can be reduced completely only at high temperatures (above 600 °C); the temperature of the reducing activation treatment plays a crucial role on the catalytic activity. HERFD-XAS and APXPS measurements show that an amorphous Ga 2 O 3 shell persists during catalysis after low temperature reductions, promoting methanol synthesis. [ABSTRACT FROM AUTHOR]

X-ray Raman spectroscopy (XRS) combined with small-angle x-ray scattering (SAXS) were used to study aqueous solutions of HCl and NaOH. Hydrated structures of H+ and OH- are not simple mirror images of each other. While both ions have been shown to strengthen local hydrogen bonds in the hydration shell as indicated by XRS, SAXS suggests that H+ and OH- have qualitatively different long-range effects. The SAXS structure factor of HCl (aq) closely resembles that of pure water, while NaOH (aq) behaves similar to NaF (aq). We propose that protons only locally enhance hydrogen bonds while hydroxide ions induce tetrahedrality in the overall hydrogen bond network of water. [ABSTRACT FROM AUTHOR]

Properties of liquid silicates under high-pressure and high-temperature conditions are critical for modeling the dynamics and solidification mechanisms of the magma ocean in the early Earth, as well as for constraining entrainment of melts in the mantle and in the present-day core–mantle boundary. Here we present in situ structural measurements by X-ray diffraction of selected amorphous silicates compressed statically in diamond anvil cells (up to 157 GPa at room temperature) or dynamically by laser-generated shock compression (up to 130 GPa and 6,000 K along the MgSiO3 glass Hugoniot). The X-ray diffraction patterns of silicate glasses and liquids reveal similar characteristics over a wide pressure and temperature range. Beyond the increase in Si coordination observed at 20 GPa, we find no evidence for major structural changes occurring in the silicate melts studied up to pressures and temperatures exceeding Earth’s core mantle boundary conditions. This result is supported by molecular dynamics calculations. Our findings reinforce the widely used assumption that the silicate glasses studies are appropriate structural analogs for understanding the atomic arrangement of silicate liquids at these high pressures. [ABSTRACT FROM AUTHOR]

Nickel-rich layered oxide cathode materials are attractive near-term candidates for boosting the energy density of next generation lithium-ion batteries. The practical implementation of these materials is, however, hindered by unsatisfactory capacity retention, poor thermal stability, and oxygen release as a consequence of structural decomposition, which may have serious safety consequences. The undesired side reactions are often exothermic, causing complicated electro-chemo-mechanical interplay at elevated temperatures. In this work, we explore the effects of thermal exposure on chemically delithiated LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC-811) at a practical state-of-charge (50% Li content) and an over-charged state (25% Li content). A systematic study using a suite of advanced synchrotron radiation characterization tools reveals the dynamics of thermal behavior of the charged NMC-811, which involves sophisticated structural and chemical evolution; e.g. lattice phase transformation, transition metal (TM) cation migration and valence change, and lithium redistribution. These intertwined processes exhibit a complex 3D spatial heterogeneity and, collectively, form a valence state gradient throughout the particles. Our study sheds light on the response of NMC-811 to elevated temperature and highlights the importance of the cathode's thermal robustness for battery performance and safety. [ABSTRACT FROM AUTHOR]

We report on measurements of the Kβ diagram, valence‐to‐core (VtC), and hypersatellite X‐ray spectra induced in metallic Cr by photon single and double K‐shell ionization. The experiment was carried out at the Stanford Synchrotron Radiation Lightsource using the seven‐crystal Johann‐type hard X‐ray spectrometer of the beamline 6‐2. For the Kβ diagram and VtC transitions, the present study confirms the line shape features observed in previous works, whereas the Khβ hypersatellite transition was found to exhibit a complex spectral line shape and a characteristic low‐energy shoulder. The energy shift of the hypersatellite relative to the parent diagram line was deduced from the measurements and compared with the result of extensive multiconfiguration Dirac–Fock (MCDF) calculations. A very good agreement between experiment and theory was found. The MCDF calculations were also used to compute the theoretical line shape of the hypersatellite. A satisfactory agreement was obtained between the overall shapes of the experimental and theoretical spectra, but deviations were observed on the low‐ and high‐energy flanks of the hypersatellite line. The discrepancies were explained by chemical effects, which were not considered in the MCDF calculations performed for isolated atoms. [ABSTRACT FROM AUTHOR]

Sulfur is sometimes called a spectroscopically silent element because there are so few tools for probing its chemistry. This paper will review how sulfur K-edge X-ray absorption spectroscopy and related methods can be used to overcome this limitation, using examples from the authors' research. X-rays from synchrotron radiation sources provide the means to study essentially any element in a variety of systems, ranging from pure compounds, to complex mixtures and even structured systems such as biological tissues. We show that sulfur K-edge X-ray absorption spectroscopy provides an important spectroscopic probe of sulfur chemistry in a range of systems, including those containing reactive species. Using a micro-focused X-ray beam, chemically-dependent X-ray fluorescence imaging can be used to image different sulfur species at a variety of spatial resolutions from microscopic to macroscopic. Increased sensitivity and deeper insights into electronic structure will be available in future studies using a suite of methods that are collectively known as advanced X-ray spectroscopy. [ABSTRACT FROM AUTHOR]

An X‐ray emission spectrometer that can detect the sulfur Kα emission lines with large throughput and a high energy resolution is presented. The instrument is based on a large d‐spacing perfect Bragg analyzer that diffracts the sulfur Kα emission at close to backscattering angles. This facilitates the application of efficient concepts routinely employed in hard X‐ray spectrometers towards the tender X‐ray regime. The instrument described in this work is based on an energy‐dispersive von Hamos geometry that is well suited for photon‐in photon‐out spectroscopy at X‐ray free‐electron laser and synchrotron sources. Comparison of its performance with previously used instrumentation is presented through measurements using sulfur‐containing species performed at the LCLS. It is shown that the overall signal intensity is increased by a factor of ∼15. Implementation of this approach in the design of a tender X‐ray spectroscopy endstation for LCLS‐II is also discussed. [ABSTRACT FROM AUTHOR]

The evolution in local structure and electronic properties of cobalt was investigated during in situ sulfurization. Using a combination of 1s X‐ray absorption (XAS) and 1s3p resonant inelastic X‐ray scattering (RIXS), the valence, coordination and symmetry of cobalt ions were tracked in two cobalt‐promoted molybdenum oxide precursors of the hydrodesulfurization catalyst system, namely Co–Mo/Al2O3 and Co–Ni–Mo/Al2O3. Extended X‐ray absorption fine structure shows that the Co—O bonds were replaced with Co—S bonds as a function of reaction temperature. The cobalt K pre‐edge intensity shows that the symmetry of cobalt was modified from Co3+Oh and Co2+Oh to a Co2+ ion where the inversion symmetry is broken, in agreement with a square‐pyramidal site. The 1s3p RIXS data revealed the presence of an intermediate cobalt oxy‐sulfide species. This species was not detected from XAS and was determined from the increased information obtained from the 1s3p RIXS data. The cobalt XAS and RIXS data show that nickel has a significant influence on the formation of the cobalt oxy‐sulfide intermediate species prior to achieving the fully sulfided state at T > 400°C. [ABSTRACT FROM AUTHOR]

Hemoglobin and myoglobin are oxygen-binding proteins with S = 0 heme {FeO2}8 active sites. The electronic structure of these sites has been the subject of much debate. This study utilizes Fe K-edge X-ray absorption spectroscopy (XAS) and 1s2p resonant inelastic X-ray scattering (RIXS) to study oxyhemoglobin and a related heme {FeO2}8 model compound, [(pfp)Fe(1-MeIm)(O2)] (pfp = meso-tetra(α,α,α,α-o-pivalamido-phenyl)porphyrin, or TpivPP, 1- MeIm = 1-methylimidazole) (pfpO2), which was previously analyzed using L-edge XAS. The K-edge XAS and RIXS data of pfpO2 and oxyhemoglobin are compared with the data for low-spin FeII and FeIII [Fe(tpp)(Im)2]0/+ (tpp = tetra-phenyl porphyrin) compounds, which serve as heme references. The X-ray data show that pfpO2 is similar to FeII, while oxyhemoglobin is qualitatively similar to FeIII, but with significant quantitative differences. Density-functional theory (DFT) calculations show that the difference between pfpO2 and oxyhemoglobin is due to a distal histidine H bond to O2 and the less hydrophobic environment in the protein, which lead to more backbonding into the O2. A valence bond configuration interaction multiplet model is used to analyze the RIXS data and show that pfpO2 is dominantly FeII with 6-8% FeIII character, while oxyhemoglobin has a very mixed wave function that has 50-77% FeIII character and a partially polarized Fe-O2 π-bond. [ABSTRACT FROM AUTHOR]

Trace element inventories are known to correlate with specific histological structures in bone, reflecting organismal physiology and life histories. By studying trace elements in fossilised bone, particularly in individuals with cyclic bone growth (alternating fast/slow bone deposition), we can improve our understanding of the physiology of extinct organisms. In this study we present the first direct comparison between optical histology (bone tissue identification) and synchrotron-based chemical mapping, quantification, and characterisation of trace elements (biochemistry) within cyclic growth tissues, in this case within bones of a cave hyaena (Crocuta crocuta spelaea). Results show distributions of zinc, an element strongly associated with active ossification and bone growth, correlating with (1) fast-growing tissue of zonal bone (cyclic growth) in an extinct hyaena and (2) secondary osteons (remodelling) in both extant and extinct hyaena. Concentrations and coordination chemistry of zinc within the fossil sample are comparable to those seen in extant bone suggesting that zinc is endogenous to the sample and that the chemistry of bone growth has been preserved for 40 ka. These results demonstrate that the study of trace elements as part of the histochemistry has wide utility for reconstructing growth, diet and other lifestyle factors in archaeological and fossil bone. [ABSTRACT FROM AUTHOR]

The bright ultrafast pulses of X-ray Free-Electron Lasers allow investigation into the structure of matter under extreme conditions. We have used single pulses to ionize and probe water as it undergoes a phase transition from liquid to plasma. We report changes in the structure of liquid water on a femtosecond time scale when irradiated by single 6.86 keV X-ray pulses of more than 106 J/cm2. These observations are supported by simulations based on molecular dynamics and plasma dynamics of a water system that is rapidly ionized and driven out of equilibrium. This exotic ionic and disordered state with the density of a liquid is suggested to be structurally different from a neutral thermally disordered state. [ABSTRACT FROM AUTHOR]

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. We observe that the mechanical breakdown of charged Li1–xNi0.4Mn0.4Co0.2O2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformations from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles, i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to the formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice. [ABSTRACT FROM AUTHOR]

Carbon compounds are ubiquitous and occur in a diversity of chemical forms in many systems including ancient and historic materials ranging from cultural heritage to paleontology. Determining their speciation cannot only provide unique information on their origin but may also elucidate degradation processes. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge (280-350 eV) is a very powerful method to probe carbon speciation. However, the short penetration depth of soft X-rays imposes stringent constraints on sample type, preparation, and analytical environment. A hard Xray probe such as X-ray Raman scattering (XRS) can overcome many of these difficulties. Here we report the use of XRS at ~6 keV incident energy to collect carbon K-edge XANES data and probe the speciation of organic carbon in several specimens relevant to cultural heritage and natural history. This methodology enables the measurement to be done in a nondestructive way, in air, and provides information that is not compromised by surface contamination by ensuring that the dominant signal contribution is from the bulk of the probed material. Using the backscattering geometry at large photon momentum transfer maximizes the XRS signal at the given X-ray energy and enhances nondipole contributions compared to conventional XANES, thereby augmenting the speciation sensitivity. The capabilities and limitations of the technique are discussed. We show that despite its small cross section, for a range of systems the XRS method can provide satisfactory signals at realistic experimental conditions. XRS constitutes a powerful complement to FT-IR, Raman, and conventional XANES spectroscopy, overcoming some of the limitations of these techniques. [ABSTRACT FROM AUTHOR]

The multifunctional protein cytochrome c (cyt c) plays key roles in electron transport and apoptosis, switching function by modulating bonding between a heme iron and the sulfur in a methionine residue. This Fe–S(Met) bond is too weak to persist in the absence of protein constraints. We ruptured the bond in ferrous cyt c using an optical laser pulse and monitored the bond reformation within the protein active site using ultrafast x-ray pulses from an x-ray free-electron laser, determining that the Fe–S(Met) bond enthalpy is ~4 kcal/mol stronger than in the absence of protein constraints. The 4 kcal/mol is comparable with calculations of stabilization effects in other systems, demonstrating how biological systems use an entatic state for modest yet accessible energetics to modulate chemical function. [ABSTRACT FROM AUTHOR]

For overall water-splitting systems, it is essential to establish O2-insensitive cathodes that allow cogeneration of H2 and O2. An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2. In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoO x/Pt/SrTiO3 with inhibited water formation from H2 and O2, which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis. [ABSTRACT FROM AUTHOR]

For overall water-splitting systems, it is essential to establish O2-insensitive cathodes that allow cogeneration of H2 and O2. An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2. In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoO x/Pt/SrTiO3 with inhibited water formation from H2 and O2, which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis. [ABSTRACT FROM AUTHOR]

A systematic investigation of the electronic structure of the CdS buffer layer of CIGS solar cells has been undertaken using S K- edge X-ray absorption spectroscopy (XAS), both experimentally and theoretically. We found from XAS that growing CdS films by chemical bath deposition (CBD) exhibits more long-range disorder when compared to single crystal CdS, CdS grown by atomic layer deposition (ALD) and theory. We investigated the significance of a variety of point defects and potential atomic substitutions in first-principles estimates of the differential S K- edge XAS sensitivity. We find that substituting some sulfur atoms with e.g. oxygen or selenium does not introduce significant changes to the partial S(3 p ) density of states of the conduction band in CdS and we infer that the electronic structure modifications of these defects are spatially localized and do not hybridize strongly with bands with significant sulfur p character. Moreover, by comparison with experimental XAS should be sensitive to CdSO 4 ; however this is not in the CdS layers of CIGS devices studied here. We also find that the CBD of CdS on FTO-glass and separately on CIGS does not produce any significant changes in the local atomic structure of CdS indicating no CIGS-influenced growth. [ABSTRACT FROM AUTHOR]

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. We used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorption spectra in CGO in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units. [ABSTRACT FROM AUTHOR]

Biological systems use copper as a redox center in many metalloproteins, where the role of the metal is to cycle between its +1 and +2 oxidation states. This chemistry requires the redox potential to be in a range that can stabilize both Cu(I) and Cu(II) states and often involves protein-derived ligand sets involving mixed histidine-methionine coordination that balance the preferences of both oxidation states. Transport proteins, on the other hand, utilize copper in the Cu(I) state and often contain sites comprised predominately of the cuprophilic residue methionine. The electronic factors that allow enzymes and transporters to balance their redox requirements are complex and are often elusive due to the dearth of spectroscopic probes of the Cu(I) state. Here we present the novel application of X-ray emission spectroscopy to copper proteins via a study of a series of mixed His-Met copper sites where the ligand set varies in a systematic way between the His3 and Met3 limits. The sites are derived from the wild-type peptidylglycine monooxygenase (PHM), two single-site variants which replicate each of its two copper sites (CuM-site and CuH-site), and the transporters CusF and CusB. Clear differences are observed in the Kβ2,5 region at the Met3 and His3 limits. CusB (Met3) has a distinct peak at 8978.4 eV with a broad shoulder at 8975.6 eV, whereas CuH (His3) has two well-resolved features: a more intense feature at 8974.8 eV and a second at 8977.2 eV. The mixed coordination sphere CusF (Met2His) and the PHM CuM variant (Met1His2) have very similar spectra consisting of two features at 8975.2 and 8977.8 eV. An analysis of DFT calculated spectra indicate that the intensity of the higher energy peak near 8978 eV is mediated by mixing of ligand-based orbitals into the Cu d10 manifold, with S from Met providing more intensity by facilitating increased Cu p-d mixing. Furthermore, reaction of WT PHM with CO (an oxygen analogue) produced the M site CO complex, which showed a unique XES spectrum that could be computationally reproduced by including interactions between Cu(I) and the CO ligand. The study suggests that the valence-to-core (VtC) region can not only serve as a probe of ligand speciation but also offer insight into the coordination geometry, in a fashion similar to XAS pre-edges, and may be sufficiently sensitive to the coordination of exogenous ligands to be useful in the study of reaction mechanisms. [ABSTRACT FROM AUTHOR]

X-ray focus optimization and characterization based on coherent scattering and quantitative speckle size measurements was demonstrated at the Linac Coherent Light Source. Its performance as a single-pulse free-electron laser beam diagnostic was tested for two typical focusing configurations. The results derived from the speckle size/shape analysis show the effectiveness of this technique in finding the focus' location, size and shape. In addition, its single-pulse compatibility enables users to capture pulse-to-pulse fluctuations in focus properties compared with other techniques that require scanning and averaging. [ABSTRACT FROM AUTHOR]

For lithium intercalation battery electrodes, understanding of the electronic structure of bulk and surface is essential for their operation and functionality. Soft X-rays are excellent probes for such electronic structure information, but soft X-rays are predominantly surface sensitive and thus cannot probe the bulk. Moreover, soft X-rays hardly permit meaningful in situ and operando studies in battery assemblies. We show here how we penetrate with hard X-rays (>10 keV) in situ a lithium cell, containing a manganite-based cathode. Through X-ray Raman spectroscopy we extract the Mn 2p multiplet from the entire cathode material, thus obtaining bulk-sensitive electronic structure information during battery charging and discharging. [ABSTRACT FROM AUTHOR]

The preservation of fossils reflects the interplay of inorganic and organic chemical processes, which should be clearly differentiated to make interpretations about the biology of extinct organisms. A new coliiformes bird (mouse bird) from the ∼50 million year old Green River Formation (Wyoming, USA) has here been analysed using synchrotron X-ray fluorescence and environmental scanning electron microscopy with an attached X-ray energy dispersive system (ESEM-EDS). The concentration and distribution of 16 elements (Si, P, S, Cl, K, Ca, Ti, Mg, Fe, Ni, Cu, Zn, As, Br, Ba, Hg) has been mapped for individual points on the sample. S, Cu and Zn map distinctly within visibly preserved feathers and X-ray Absorption Spectroscopy (XAS) shows that S and Cu within the feathers are organically bound in a similar manner to modern feathers. The morphological preservation of the feathers, on both macro- and microscopic scales, is variable throughout the fossil and the differences in the lateral microfacies have resulted in a morphological preservation gradient. This study clearly differentiates endogenous organic remains from those representing exogenous overprinted geochemical precipitates and illustrates the chemical complexity of the overall taphonomic process. [ABSTRACT FROM AUTHOR]

Highly active catalysts for the oxygen evolution reaction (OER) are required for the development of photoelectrochemical devices that generate hydrogen efficiently from water using solar energy. Here, we identify the origin of a 500-fold OER activity enhancement that can be achieved with mixed (Ni,Fe)oxyhydroxides (Ni1-xFexOOH) over their pure Ni and Fe parent compounds, resulting in one of the most active currently known OER catalysts in alkaline electrolyte. Operando X-ray absorption spectroscopy (XAS) using high energy resolution fluorescence detection (HERFD) reveals that Fe3+ in Ni1-xFexOOH occupies octahedral sites with unusually short Fe--O bond distances, induced by edge-sharing with surrounding [NiO6] octahedra. Using computational methods, we establish that this structural motif results in near optimal adsorption energies of OER intermediates and low overpotentials at Fe sites. By contrast, Ni sites in Ni1-xFexOOH are not active sites for the oxidation of water. [ABSTRACT FROM AUTHOR]

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnOx, a promising OER catalyst. We conclusively demonstrate that adding Au to MnOx significantly enhances OER activity relative to MnOx in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnOx catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnOx that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnOx. [ABSTRACT FROM AUTHOR]

Self-doping of cations on the tetrahedraland octahedral sitesin spinel oxides creates “anti-site” defects, whichresults in functional optical, electronic, magnetic, and other materialsproperties. Previously, we divded the III–II spinel familyinto four doping types (DTs) based on first-principle calculationsin order to understand their electrical behavior. Here, we presentexperimental evidence on two prototype spinels for each major dopingtype (DT1 and DT4) that test the first principles calculations. Forthe DT-1 Ga2ZnO4spinel, we show that the anti-sitedefects in a stoichiometric film are equal in concentration and compenstateeach other, whereas, for nonstoichiometric Cr2MnO4, a representative DT-4 spinel, excess Mn on the tetrahedral sitesbecomes electrically inactive as the Mn species switch from (III)to (II). The agreement between experiment and theory validates theDoping Rules distilled from the theoretical framework and significantlyenhances our understanding of the defect chemistry of spinel oxides. [ABSTRACT FROM AUTHOR]

The protonation state of oxo bridges in nature is of profound importance for a variety of enzymes, including the Mn4CaO5 cluster of photosystem II and the Mn2O2 cluster in Mn catalase. A set of dinuclear bis-μ-oxo-bridged MnIV complexes in different protonation states was studied by Kβ emission spectroscopy to form the foundation for unraveling the protonation states in the native complex. The valence-to-core regions (valence-to-core XES) of the spectra show significant changes in intensity and peak position upon protonation. DFT calculations were performed to simulate the valence-to-core XES spectra and to assign the spectral features to specific transitions. The Kβ2,5 peaks arise primarily from the ligand 2p to Mn 1s transitions, with a characteristic low energy shoulder appearing upon oxo-bridge protonation. The satellite Κβ peak provides a more direct signature of the protonation state change, since the transitions originating from the 2s orbitals of protonated and unprotonated μ-oxo bridges dominate this spectral region. The energies of the Κβ features differ by 3 eV and thus are well resolved in the experimental spectra. Additionally, our work explores the chemical resolution limits of the method, namely, whether a mixed (μ-O)(μ-OH2) motif can be distinguished from a symmetric (μ-OH)2 one. The results reported here highlight the sensitivity of Kβ valence-to-core XES to single protonation state changes of bridging ligands, and form the basis for further studies of oxo-bridged polymetallic complexes and metalloenzyme active sites. In a complementary paper, the results from X-ray absorption spectroscopy of the same MnIV dimer series are discussed. [ABSTRACT FROM AUTHOR]

Charles Darwin acknowledged the importance of colour in the natural selection of bird plumage. Colour can indicate age, sex, and diet, as well as play roles in camouflage, mating and establishing territories. Feather and integument colour depend on both chemical and structural characteristics and so melanosome structure and trace metal biomarkers can be used to infer colour and pigment patterns in a range of extant and fossil organisms. In this study, three key specimens of Archaeopteryx were subjected to non-destructive chemical analysis in order to investigate the potential preservation of original pigmentation in early fossil feathers. Synchrotron Rapid Scanning X-ray Fluorescence (SRS-XRF) maps are combined with sulphur X-ray Absorption Near Edge Structure (XANES) spectroscopy to provide the first map of organic sulphur distribution within whole fossils, and demonstrate that organically derived endogenous compounds are present. The distribution of trace-metals and organic sulphur in Archaeopteryx strongly suggests that remnants of endogenous eumelanin pigment have been preserved in the feathers of this iconic fossil. These distributions are used here to predict the complete feather pigment pattern and show that the distal tips and outer vanes of feathers were more heavily pigmented than inner vanes, contrary to recent studies. This pigment adaptation might have impacted upon the structural and mechanical properties of early feathers, steering plumage evolution in Archaeopteryx and other feathered theropod dinosaurs. [ABSTRACT FROM AUTHOR]