Iron Kß X-ray Emission Spectroscopy: The Origin of Spectral Features from Atomic to Molecular Systems Using Multi-configurational Calculations.

Kß X-ray emission spectroscopy (XES) is widely used to fingerprint the local spin of transition-metal ions, including in pump-probe experiments, to identify excited states or in chemical and biological reactions to characterize short-lived intermediates. In this study, the spectra of ferrous and ferric complexes for various spin states were measured experimentally and described theoretically through restricted active space (RAS) calculations including dynamic correlations. Through the RAS calculations from simple atomic models to complex molecular systems, spectral effects such as the exchange interactions, crystal-field strength, and covalent orbital mixing were evaluated and discussed. The calculations find that only the spectral features of low-spin cases show a dependence on the crystal-field strength, particularly for ferrous low spin. The effect of the covalent orbital mixing strength on the first moment of the Kß1,3 main line and the Kß1,3-Kß' energy splitting is quantitatively described. Clear relationships are found within a given nominal spin but less between different spin states, which calls for careful selection of reference spectra in future experiments. This study further advances our understanding of the correlation between changes in experimental spectral features and their corresponding electronic structure information.

A versatile pressure-cell design for studying ultrafast molecular-dynamics in supercritical fluids using coherent multi-pulse x-ray scattering.

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.

Synchrotron speciation of umbilical cord mercury and selenium after environmental exposure in Niigata.

The insidious and deadly nature of mercury's organometallic compounds is informed by two large scale poisonings due to industrial mercury pollution that occurred decades ago in Minamata and Niigata, Japan. The present study examined chemical speciation for both mercury and selenium in a historic umbilical cord sample from a child born to a mother who lived near the Agano River in Niigata. The mother had experienced mercury exposure leading to more than 50 ppm mercury measured in her hair and was symptomatic 9 years prior to the birth. We sought to determine the mercury and selenium speciation in the child's cord using Hg Lα1 and Se Kα1 high-energy resolution fluorescence detected X-ray absorption spectroscopy, the chemical speciation of mercury was found to be predominantly organometallic and coordinated to a thiolate. The selenium was found to be primarily in an organic form and at levels higher than those of mercury, with no evidence of mercury-selenium chemical species. Our results are consistent with mercury exposure at Niigata being due to exposure to organometallic mercury species.

A multimodal flow reactor for photocatalysis under atmospheric conditions.

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.

Tracking Active Phase Behavior on Boron Nitride during the Oxidative Dehydrogenation of Propane Using Operando X-ray Raman Spectroscopy.

Hexagonal boron nitride (hBN) is a highly selective catalyst for the oxidative dehydrogenation of propane (ODHP) to propylene. Using a variety of ex situ characterization techniques, the activity of the catalyst has been attributed to the formation of an amorphous boron oxyhydroxide surface layer. The ODHP reaction mechanism proceeds via a combination of surface mediated and gas phase propagated radical reactions with the relative importance of both depending on the surface-to-void-volume ratio. Here we demonstrate the unique capability of operando X-ray Raman spectroscopy (XRS) to investigate the oxyfunctionalization of the catalyst under reaction conditions (1 mm outer diameter reactor, 500 to 550 °C, P = 30 kPa C3H8, 15 kPa O2, 56 kPa He). We probe the effect of a water cofeed on the surface of the activated catalyst and find that water removes boron oxyhydroxide from the surface, resulting in a lower reaction rate when the surface reaction dominates and an enhanced reaction rate when the gas phase contribution dominates. Computational description of the surface transformations at an atomic-level combined with high precision XRS spectra simulations with the OCEAN code rationalize the experimental observations. This work establishes XRS as a powerful technique for the investigation of light element-containing catalysts under working conditions.

Solution phase high repetition rate laser pump x-ray probe picosecond hard x-ray spectroscopy at the Stanford Synchrotron Radiation Lightsource.

We present a dedicated end-station for solution phase high repetition rate (MHz) picosecond hard x-ray spectroscopy at beamline 15-2 of the Stanford Synchrotron Radiation Lightsource. A high-power ultrafast ytterbium-doped fiber laser is used to photoexcite the samples at a repetition rate of 640 kHz, while the data acquisition operates at the 1.28 MHz repetition rate of the storage ring recording data in an alternating on-off mode. The time-resolved x-ray measurements are enabled via gating the x-ray detectors with the 20 mA/70 ps camshaft bunch of SPEAR3, a mode available during the routine operations of the Stanford Synchrotron Radiation Lightsource. As a benchmark study, aiming to demonstrate the advantageous capabilities of this end-station, we have conducted picosecond Fe K-edge x-ray absorption spectroscopy on aqueous [FeII(phen)3]2+, a prototypical spin crossover complex that undergoes light-induced excited spin state trapping forming an electronic excited state with a 0.6-0.7 ns lifetime. In addition, we report transient Fe Kß main line and valence-to-core x-ray emission spectra, showing a unique detection sensitivity and an excellent agreement with model spectra and density functional theory calculations, respectively. Notably, the achieved signal-to-noise ratio, the overall performance, and the routine availability of the developed end-station have enabled a systematic time-resolved science program using the monochromatic beam at the Stanford Synchrotron Radiation Lightsource.

Ultrafast x-ray detection of low-spin iron in molten silicate under deep planetary interior conditions.

The spin state of Fe can alter the key physical properties of silicate melts, affecting the early differentiation and the dynamic stability of the melts in the deep rocky planets. The low-spin state of Fe can increase the affinity of Fe for the melt over the solid phases and the electrical conductivity of melt at high pressures. However, the spin state of Fe has never been measured in dense silicate melts due to experimental challenges. We report detection of dominantly low-spin Fe in dynamically compressed olivine melt at 150 to 256 gigapascals and 3000 to 6000 kelvin using laser-driven shock wave compression combined with femtosecond x-ray diffraction and x-ray emission spectroscopy using an x-ray free electron laser. The observation of dominantly low-spin Fe supports gravitationally stable melt in the deep mantle and generation of a dynamo from the silicate melt portion of rocky planets.

Unraveling Metal-Ligand Bonding in an HNO-Evolving {FeNO}6 Complex with a Combined X-ray Spectroscopic Approach.

Photolytic delivery of nitric oxide and nitroxide has substantial biomedical and phototherapeutic applications. Here, we utilized hard X-ray spectroscopic methods to identify key geometric and electronic structural features of two photolabile {FeNO}6 complexes where the compounds differ in the presence of a pendant thiol in [Fe(NO)(TMSPS2)(TMSPS2H)] and thioether in [Fe(NO)(TMSPS2)(TMSPS2CH3)] with the former complex being the only transition metal system to photolytically generate HNO. Fe Kß XES identifies the photoreactant systems as essentially Fe(II)-NO+, while valence-to-core XES extracts a NO oxidation state of +0.5. Finally, the pre-edge of the Fe high-energy-resolution fluorescence detected (HERFD) XAS spectra is shown to be acutely sensitive to perturbation of the Fe-NO covalency enhanced by the 3d-4p orbital mixing dipole intensity contribution. Collectively, this X-ray spectroscopic approach enables future time-resolved insights in these systems and extensions to other challenging redox noninnocent {FeNO}x systems.

X-ray Spectroscopic Study of the Electronic Structure of a Trigonal High-Spin Fe(IV)═O Complex Modeling Non-Heme Enzyme Intermediates and Their Reactivity.

Fe K-edge X-ray absorption spectroscopy (XAS) has long been used for the study of high-valent iron intermediates in biological and artificial catalysts. 4p-mixing into the 3d orbitals complicates the pre-edge analysis but when correctly understood via 1s2p resonant inelastic X-ray scattering and Fe L-edge XAS, it enables deeper insight into the geometric structure and correlates with the electronic structure and reactivity. This study shows that in addition to the 4p-mixing into the 3dz2 orbital due to the short iron-oxo bond, the loss of inversion in the equatorial plane leads to 4p mixing into the 3dx2-y2,xy, providing structural insight and allowing the distinction of 6- vs 5-coordinate active sites as shown through application to the Fe(IV)═O intermediate of taurine dioxygenase. Combined with O K-edge XAS, this study gives an unprecedented experimental insight into the electronic structure of Fe(IV)═O active sites and their selectivity for reactivity enabled by the π-pathway involving the 3dxz/yz orbitals. Finally, the large effect of spin polarization is experimentally assigned in the pre-edge (i.e., the α/ß splitting) and found to be better modeled by multiplet simulations rather than by commonly used time-dependent density functional theory.

Kß X-ray Emission Spectroscopy of Cu(I)-Lytic Polysaccharide Monooxygenase: Direct Observation of the Frontier Molecular Orbital for H2O2 Activation.

Lytic polysaccharide monooxygenases (LPMOs) catalyze the degradation of recalcitrant carbohydrate polysaccharide substrates. These enzymes are characterized by a mononuclear Cu(I) active site with a three-coordinate T-shaped "His-brace" configuration including the N-terminal histidine and its amine group as ligands. This study explicitly investigates the electronic structure of the d10 Cu(I) active site in a LPMO using Kß X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the 3d/p mixing required for intensity in the Kß valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kß XES data are correlated to density functional theory (DFT) calculations to define the bonding, and in particular, the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H2O2 O-O bond and understand the contribution of this FMO to the low barrier of this reaction and how the geometric and electronic structure of the Cu(I)-LPMO site is activated for rapid reactivity with H2O2.

Uncovering the 3d and 4d Electronic Interactions in Solvated Ru Complexes with 2p3d Resonant Inelastic X-ray Scattering.

The electronic structure and dynamics of ruthenium complexes are widely studied given their use in catalytic and light-harvesting materials. Here we investigate three model Ru complexes, [RuIII(NH3)6]3+, [RuII(bpy)3]2+, and [RuII(CN)6]4-, with L3-edge 2p3d resonant inelastic X-ray scattering (RIXS) to probe unoccupied 4d valence orbitals and occupied 3d orbitals and to gain insight into the interactions between these levels. The 2p3d RIXS maps contain a higher level of spectral information than the L3 X-ray absorption near edge structure (XANES). This study provides a direct measure of the 3d spin-orbit splittings of 4.3, 4.0, and 4.1 eV between the 3d5/2 and 3d3/2 orbitals of the [RuIII(NH3)6]3+, [RuII(bpy)3]2+, and [RuII(CN)6]4- complexes, respectively.

Energy conversion and storage via photoinduced polarization change in non-ferroelectric molecular [CoGa] crystals.

To alleviate the energy and environmental crisis, in the last decades, energy harvesting by utilizing optical control has emerged as a promising solution. Here we report a polar crystal that exhibits photoenergy conversion and energy storage upon light irradiation. The polar crystal consists of dinuclear [CoGa] molecules, which are oriented in a uniform direction inside the crystal lattice. Irradiation with green light induces a directional intramolecular electron transfer from the ligand to a low-spin CoIII centre, and the resultant light-induced high-spin CoII excited state is trapped at low temperature, realizing energy storage. Additionally, electric current release is observed during relaxation from the trapped light-induced metastable state to the ground state, because the intramolecular electron transfer in the relaxation process is accompanied with macroscopic polarization switching at the single-crystal level. It demonstrates that energy storage and conversion to electrical energy is realized in the [CoGa] crystals, which is different from typical polar pyroelectric compounds that exhibit the conversion of thermal energy into electricity.

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kß main line and valence-to-core x-ray emission spectroscopy.

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kß main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kß main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

The Local Electronic Structure of Supercritical CO2 from X-ray Raman Spectroscopy and Atomistic-Scale Modeling.

Supercritical CO2 is encountered in several technical and natural systems related to biology, geophysics, and engineering. While the structure of gaseous CO2 has been studied extensively, the properties of supercritical CO2, particularly close to the critical point, are not well-known. In this work, we combine X-ray Raman spectroscopy, molecular dynamics simulations, and first-principles density functional theory (DFT) calculations to characterize the local electronic structure of supercritical CO2 at conditions around the critical point. The X-ray Raman oxygen K-edge spectra manifest systematic trends associated with the phase change of CO2 and the intermolecular distance. Extensive first-principles DFT calculations rationalize these observations on the basis of the 4sσ Rydberg state hybridization. X-ray Raman spectroscopy is found to be a sensitive tool for characterizing electronic properties of CO2 under challenging experimental conditions and is demonstrated to be a unique probe for studying the electronic structure of supercritical fluids.

Sulfur X-ray Absorption and Emission Spectroscopy of Organic Sulfones.

The sulfones are a widespread group of organo-sulfur compounds, which contain the sulfonyl SO2 group attached to two carbons and have a formal sulfur oxidation state of +2. We have examined the sulfur K near-edge X-ray absorption spectroscopy (XAS) of a range of different sulfones and find substantial spectroscopic variability depending upon the nature of the coordination to the sulfonyl group. We have also examined the sulfur Kß X-ray emission spectroscopy (XES) of selected representative sulfones. Density functional theory simulations show satisfactory reproduction of both absorption and emission spectra while enabling assignment of the various transitions comprising the spectra. The correspondence between observed and simulated spectra shows promise for ab initio prediction of sulfur X-ray absorption and emission spectra of sulfones of any substituent. The absorption spectra and, to a lesser extent, the emission spectra are sensitive to the nature of the organic groups bound to the sulfonyl (SO2) moiety, clearly showing the potential of X-ray spectroscopy as an in situ probe of sulfone chemistry.

Understanding the Stability of Manganese Chromium Antimonate Electrocatalysts through Multimodal In Situ and Operando Measurements.

Improving electrocatalyst stability is critical for the development of electrocatalytic devices. Herein, we utilize an on-line electrochemical flow cell coupled with an inductively coupled plasma-mass spectrometer (ICP-MS) to characterize the impact of composition and reactant gas on the multielement dissolution of Mn(-Cr)-Sb-O electrocatalysts. Compared to Mn2O3 and Cr2O3 oxides, the antimonate framework stabilizes Mn at OER potentials and Cr at both ORR and OER potentials. Furthermore, dissolution of Mn and Cr from Mn(-Cr) -Sb-O is driven by the ORR reaction rate, with minimal dissolution under N2. We observe preferential dissolution of Cr totaling 13% over 10 min at 0.3, 0.6, and 0.9 V vs RHE, with only 1.5% loss of Mn, indicating an enrichment of Mn at the surface of the particles. Despite this asymmetric dissolution, operando X-ray absorption spectroscopy (XAS) showed no measurable changes in the Mn K-edge at comparable potentials. This could suggest that modification to the Mn oxidation state and/or phase in the surface layer is too small or that the layer is too thin to be measured with the bulk XAS measurement. Lastly, on-line ICP-MS was used to assess the effects of applied potential, scan rate, and current on Mn-Cr-Sb-O during cyclic voltammetry and accelerated stress tests. With this deeper understanding of the interplay between oxygen reduction and dissolution, testing procedures were identified to maximize both activity and stability. This work highlights the use of multimodal in situ characterization techniques in tandem to build a more complete model of stability and develop protocols for optimizing catalyst performance.

Investigating the electronic structure of high explosives with X-ray Raman spectroscopy.

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 ([Formula: see text] 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.

Alzheimer's Drug PBT2 Interacts with the Amyloid ß 1-42 Peptide Differently than Other 8-Hydroxyquinoline Chelating Drugs.

Although Alzheimer's disease (AD) was first described over a century ago, it remains the leading cause of age-related dementia. Innumerable changes have been linked to the pathology of AD; however, there remains much discord regarding which might be the initial cause of the disease. The "amyloid cascade hypothesis" proposes that the amyloid ß (Aß) peptide is central to disease pathology, which is supported by elevated Aß levels in the brain before the development of symptoms and correlations of amyloid burden with cognitive impairment. The "metals hypothesis" proposes a role for metal ions such as iron, copper, and zinc in the pathology of AD, which is supported by the accumulation of these metals within amyloid plaques in the brain. Metals have been shown to induce aggregation of Aß, and metal ion chelators have been shown to reverse this reaction in vitro. 8-Hydroxyquinoline-based chelators showed early promise as anti-Alzheimer's drugs. Both 5-chloro-7-iodo-8-hydroxyquinoline (CQ) and 5,7-dichloro-2-[(dimethylamino)methyl]-8-hydroxyquinoline (PBT2) underwent unsuccessful clinical trials for the treatment of AD. To gain insight into the mechanism of action of 8HQs, we have investigated the potential interaction of CQ, PBT2, and 5,7-dibromo-8-hydroxyquinoline (B2Q) with Cu(II)-bound Aß(1-42) using X-ray absorption spectroscopy (XAS), high energy resolution fluorescence detected (HERFD) XAS, and electron paramagnetic resonance (EPR). By XAS, we found CQ and B2Q sequestered ∼83% of the Cu(II) from Aß(1-42), whereas PBT2 sequestered only ∼59% of the Cu(II) from Aß(1-42), suggesting that CQ and B2Q have a higher relative Cu(II) affinity than PBT2. From our EPR, it became clear that PBT2 sequestered Cu(II) from a heterogeneous mixture of Cu(II)Aß(1-42) species in solution, leaving a single Cu(II)Aß(1-42) species. It follows that the Cu(II) site in this Cu(II)Aß(1-42) species is inaccessible to PBT2 and may be less solvent-exposed than in other Cu(II)Aß(1-42) species. We found no evidence to suggest that these 8HQs form ternary complexes with Cu(II)Aß(1-42).

A new µ-high energy resolution fluorescence detection microprobe imaging spectrometer at the Stanford Synchrotron Radiation Lightsource beamline 6-2.

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.

X-ray Raman Scattering: A Hard X-ray Probe of Complex Organic Systems.

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.