Anomalous Scattering Research Articles

Anomalous Frequency and Temperature Dependent Scattering in the Dilute Metallic Phase in Lightly Doped SrTiO_{3}.

The mechanism of superconductivity in materials with aborted ferroelectricity and its emergence out of a dilute metallic phase in systems like doped SrTiO_{3} is an outstanding issue in condensed matter physics. This dilute metal has anomalous properties that are both similar and different to those found in the normal state of other unconventional superconductors. For instance, T^{2} resistivity can be found at densities that are too small to allow current decay through electron-electron scattering. We have investigated the optical properties of the dilute metallic phase in doped SrTiO_{3} using THz time-domain spectroscopy. At low frequencies the THz response exhibits a Drude-like form as expected for typical metal-like conductivity. We observed the frequency and temperature dependencies to the low energy scattering rate Γ(ω,T)∝(ℏω)^{2}+(pπk_{B}T)^{2} expected in a conventional Fermi liquid. However, we find the lowest known p values of 0.39-0.72. As p is 2 in a canonical Fermi liquid and existing models based on energy dependent elastic scattering bound p from below to 1, our observation lies outside current explanation. Our data also give insight into the high temperature regime and show that the temperature dependence of the resistivity derives in part from strong T dependent mass renormalizations.

DSAS: a new macromolecular substructure solution program based on the modified phase-retrieval algorithm

Abstract Considering the pivotal role of single-wavelength anomalous diffraction (SAD) in macromolecular crystallography, our objective was to introduce DSAS, a novel program designed for efficient anomalous scattering substructure determination. DSAS stands out with its core components: a modified phase-retrieval algorithm and automated parameter tuning. The software boasts an intuitive graphical user interface (GUI), facilitating seamless input of essential data and real-time monitoring. Extensive testing on DSAS has involved diverse datasets, encompassing proteins, nucleic acids, and various anomalous scatters such as sulfur (S), selenium (Se), metals, and halogens. The results confirm DSAS's exceptional performance in accurately determining heavy atom positions, making it a highly effective tool in the field.

High-Throughput Interactome Determination via Sulfur Anomalous Scattering.

We propose a novel approach for detecting the binding between proteins making use of the anomalous diffraction of natively present heavy elements, e.g., sulfurs, inside molecular three-dimensional structures. In particular, we analytically and numerically show that the diffraction patterns produced by the anomalous scattering of the sulfur atoms in a given direction depend additively on the relative distances between all couples of sulfur atoms. Thus, the differences in the patterns produced by bound proteins with respect to their nonbonded states can be exploited to rapidly assess protein complex formation. On the basis of our results, we suggest a possible experimental procedure for detecting protein-protein binding. Overall, the completely label-free and rapid method we propose may be readily extended to probe interactions on a large scale, thus paving the way for the development of a novel field of research based on a synchrotron light source.

Anomalous Small-Angle X-ray Scattering and Its Application in the Dynamic Reconstruction of Electrochemical CO2 Reduction Catalysts

The electrochemical CO2 reduction reaction (CO2RR) is a promising approach for mitigating the greenhouse effect arising from anthropogenic CO2 emission. Nonetheless, poor product selectivity associated with electrochemical catalysts is the main technical problem for the application of CO2RR technology. The catalytic performance of nano-catalysts is strongly dependent on their microstructural features. Anomalous small-angle X-ray scattering (ASAXS) is one of the most effective techniques for studying nanostructural change in an operando way, especially for complex systems and mixed-element catalyst situations. Furthermore, based on the research results of ASAXS, appropriate catalyst components and nanostructures can be designed to achieve stable catalytic performance of the catalyst, promote catalytic reaction rate, or improve catalytic reaction selectivity. In this paper, the basic concept, principle, and applications in different systems of ASAXS are reviewed thoroughly. Finally, the development prospect of ASAXS in the field of electrocatalysis is prospected. It is hoped that this review will further promote ASAXS technology to play a more far-reaching impact in the field of electrocatalytic CO2RR.

Theory of Generation of Anomalous Scattering Spectra in Not-Dense Plasma under Conditions of Electron Cyclotron Microwave Heating at the Second Resonance Harmonic

Theory of Generation of Anomalous Scattering Spectra in Not-Dense Plasma under Conditions of Electron Cyclotron Microwave Heating at the Second Resonance Harmonic

Evaluation of Semiconductors using Anomalous X-ray Scattering (2)

Evaluation of Semiconductors using Anomalous X-ray Scattering (2)

Extending the novel |ρ|-based phasing algorithm to the solution of anomalous scattering substructures from SAD data of protein crystals.

Owing to the importance of the single-wavelength anomalous diffraction (SAD) technique, the recently developed |ρ|-based phasing algorithm (SM,|ρ|) incorporating the inner-pixel preservation (ipp) procedure [Rius & Torrelles (2021). Acta Cryst A77, 339-347] has been adapted to the determination of anomalous scattering substructures and its applicability tested on a series of 12 representative experimental data sets, mostly retrieved from the Protein Data Bank. To give an idea of the suitability of the data sets, the main indicators measuring their quality are also given. The dominant anomalous scatterers are either SeMet or S atoms, or metals/clusters incorporated by soaking. The resulting SAD-adapted algorithm solves the substructures of the test protein crystals quite efficiently.

On the Issue of the Possibility of Studying Anomalous Scattering of Microwave Beams of Ordinary Polarization in Plasma of Edge Transport Barrier in the T-15MD Tokamak

On the Issue of the Possibility of Studying Anomalous Scattering of Microwave Beams of Ordinary Polarization in Plasma of Edge Transport Barrier in the T-15MD Tokamak

A Statistical Study of Auroral Medium Frequency Bursts and Anomalous Incoherent Scatter Radar Echoes

AbstractDifferent types of incoherent scatter radar (ISR) echoes are observed associated with aurora, including some which have been interpreted as signatures of cavitating Langmuir turbulence (CLT). Akbari et al. (2013) https://doi.org/10.1002/jgra.50314 discussed two instances of correlation between CLT and naturally occurring radio emissions called medium frequency burst (MFB) which occur at substorm onsets. Based on that observation, radio detections of MFB from Toolik Lake Observatory have been applied to investigate occurrence of CLT in ISR data from Poker Flat Incoherent Scatter Radar and their possible correlation with MFB. Of 131 MFB events, 25 occurred within 15 min of an ISR echo detection, compared to 6 of 116 intervals of a control set with similar local time and seasonal distribution. The difference is significant at the 10−4 level, suggesting that ISR echoes are more probable during substorm onset times identified using MFB as a proxy. However, only four observed ISR echoes coincident with one MFB event showed both specific characteristics consistent with CLT. Furthermore, investigation of the angle of arrival of MFB suggests that the electromagnetic emissions do not originate from the plasma volume where the ISR detects the echoes. The small number of coincident ISR echoes and MFB is expected due to the different volumes in which the emissions and the echoes are detected. 50% of the MFB events occurred within 20 min of a substorm onset independently identified versus 8% of the control set intervals, confirming the correlation of MFB with substorm onsets.

Formation of Iron Oxide Nanoparticles in the Internal Cavity of Ferritin-Like Dps Protein: Studies by Anomalous X-Ray Scattering

DNA-binding protein from starved cells (Dps) takes a special place among dodecamer mini-ferritins. Its most important function is protection of bacterial genome from various types of destructive external factors via in cellulo Dps–DNA co-crystallization. This protective response results in the emergence of bacterial resistance to antibiotics and other drugs. The protective properties of Dps have attracted a significant attention of researchers. However, Dps has another equally important functional role. Being a ferritin-like protein, Dps acts as an iron depot and protects bacterial cells from the oxidative damage initiated by the excess of iron. Here we investigated formation of iron oxide nanoparticles in the internal cavity of the Dps dodecamer. We used anomalous small-angle X-ray scattering as the main research technique, which allows to examine the structure of metal-containing biological macromolecules and to analyze the size distribution of metal nanoparticles formed in them. The contributions of protein and metal components to total scattering were distinguished by varying the energy of the incident X-ray radiation near the edge of the metal atom absorption band (the K-band for iron). We examined Dps specimens containing 50, 500, and 2000 iron atoms per protein dodecamer. Analysis of the particle size distribution showed that, depending on the iron content in the solution, the size of the nanoparticles formed inside the protein molecule was 2 to 4 nm and the growth of metal nanoparticles was limited by the size of the protein inner cavity. We also found some amount of iron ions in the Dps surface layer. This layer is very important for the protein to perform its protective functions, since the surface-located N-terminal domains determine the nature of interactions between Dps and DNA. In general, the results obtained in this work can be useful for the next step in studying the Dps phenomenon, as well as in creating biocompatible and solution-stabilized metal nanoparticles.

Structurally Precise Two-Transition-Metal Water Oxidation Catalysts: Quantifying Adjacent 3d Metals by Synchrotron X-Radiation Anomalous Dispersion Scattering.

Mixed 3d metal oxides are some of the most promising water oxidation catalysts (WOCs), but it is very difficult to know the locations and percent occupancies of different 3d metals in these heterogeneous catalysts. Without such information, it is hard to quantify catalysis, stability, and other properties of the WOC as a function of the catalyst active site structure. This study combines the site selective synthesis of a homogeneous WOC with two adjacent 3d metals, [Co2Ni2(PW9O34)2]10- (Co2Ni2P2) as a tractable molecular model for CoNi oxide, with the use of multiwavelength synchrotron X-radiation anomalous dispersion scattering (synchrotron XRAS) that quantifies both the location and percent occupancy of Co (∼97% outer-central-belt positions only) and Ni (∼97% inner-central-belt positions only) in Co2Ni2P2. This mixed-3d-metal complex catalyzes water oxidation an order of magnitude faster than its isostructural analogue, [Co4(PW9O34)2]10- (Co4P2). Four independent and complementary lines of evidence confirm that Co2Ni2P2 and Co4P2 are the principal WOCs and that Co2+(aq) is not. Density functional theory (DFT) studies revealed that Co4P2 and Co2Ni2P2 have similar frontier orbitals, while stopped-flow kinetic studies and DFT calculations indicate that water oxidation by both complexes follows analogous multistep mechanisms, including likely Co-OOH formation, with the energetics of most steps being lower for Co2Ni2P2 than for Co4P2. Synchrotron XRAS should be generally applicable to active-site-structure-reactivity studies of multi-metal heterogeneous and homogeneous catalysts.

Physics-driven learning of Wasserstein GAN for density reconstruction in dynamic tomography.

Object density reconstruction from projections containing scattered radiation and noise is of critical importance in many applications. Existing scatter correction and density reconstruction methods may not provide the high accuracy needed in many applications and can break down in the presence of unmodeled or anomalous scatter and other experimental artifacts. Incorporating machine-learning models could prove beneficial for accurate density reconstruction, particularly in dynamic imaging, where the time evolution of the density fields could be captured by partial differential equations or by learning from hydrodynamics simulations. In this work, we demonstrate the ability of learned deep neural networks to perform artifact removal in noisy density reconstructions, where the noise is imperfectly characterized. We use a Wasserstein generative adversarial network (WGAN), where the generator serves as a denoiser that removes artifacts in densities obtained from traditional reconstruction algorithms. We train the networks from large density time-series datasets, with noise simulated according to parametric random distributions that may mimic noise in experiments. The WGAN is trained with noisy density frames as generator inputs, to match the generator outputs to the distribution of clean densities (time series) from simulations. A supervised loss is also included in the training, which leads to an improved density restoration performance. In addition, we employ physics-based constraints such as mass conservation during the network training and application to further enable highly accurate density reconstructions. Our preliminary numerical results show that the models trained in our frameworks can remove significant portions of unknown noise in density time-series data.

Tunable Anomalous Scattering and Negative Asymmetry Parameter in a Gain-Functionalized Low Refractive Index Sphere.

Usually, low refractive index passive spheres exhibit strong forward scattering and a positive asymmetry parameter due to weak interference between the electric and magnetic scattering channels. In this work, we investigate, analytically and numerically, the forward scattering of light by a gain-functionalized low refractive index dielectric sphere. It is shown that by tuning the optical gain one can optimize the interference, which provides a novel paradigm to achieve the zero forward scattering and negative asymmetry parameter even for a low refractive index sphere. As a result, a low-density collection of such identical back scatterers provides an anomalous regime, where the scattering mean free path and extinction mean free path are greater than the transport mean free path. Furthermore, we also provide the numerical guideline to achieve the larger extinction mean free path without achieving preferential back-scattering.

Nucleation mechanisms in a SiO2-Li2O-P2O5-ZrO2 biomedical glass-ceramic: Insights on crystallisation, residual glasses and Zr4+ structural environment

In manufacturing reliable glass-ceramics, bulk chemistry and appropriate thermal treatments are critical points. To better understand the influence of nucleation parameters on the crystallisation behaviour and mechanical properties of multicomponent glass-ceramics, we studied the effects of time and temperature on phase stabilisation, the evolution of the crystal phases and physical properties of a Zr-rich lithium-silicate having a SiO2/Li2O molar ratio < 2. Here, we also provide insights into the structural environment of Zr4+ at the early stage of nucleation by Anomalous X-ray Scattering (AXS). By reverse-engineering a commercial material through remelting and sequential thermal treatments, we observed the strong effect of the nucleation temperature on the final mineral assemblage and of the volume fractions of the lithium-disilicate phase on the fracture toughness (KIc). Indeed, the KIc value was increased from ∼0.8 MPa.m½ in the pristine glass up to ∼ 2 MPa.m½, if compared to the original commercial material exhibiting a KIc value of 1.6 MPa.m½. Furthermore, the synthesis of residual glasses at different stages of the thermal treatments allowed us to observe the changes in the glass network structure and properties. AXS was used to extract the contribution exclusively coming from Zr for different nucleation steps. The differential pair distribution functions ΔZrg(r) show two distinct peaks at ∼2.10 Å and 3.44 Å, respectively associated with Zr-O and Zr-Zr/Zr-Si correlations with the formation of edge sharing in addition to corner sharing polyhedra. It was discerned the occurrence of (sub)nano-sized clusters enriched in Zr. These local clusters do not show changes during the different thermal treatments, either for higher temperatures or longer times. No Zr phases are stabilised in the crystallised materials, suggesting that these clusters do not evolve above the critical nucleus size. All evidence points to a highly heterogeneous environment and the coexistence of three structural regions i) (sub)nano Zr-clusters, ii) P enriched μ-areas, iii) residual silicate glass. The evolution and spatial distribution of these units influence the final properties.

Pinpointing and Quantifying the Aluminum Distribution in Zeolite Catalysts Using Anomalous Scattering at the Al Absorption Edge.

The location of aluminum in a zeolite framework structure defines the accessibility and geometry of the catalytically active sites, but determining this location crystallographically is fraught with difficulties. Typical zeolite catalysts contain only a small amount of aluminum, and the X-ray scattering factors for silicon and aluminum are very similar. To address this problem, we have exploited the properties of resonant X-ray powder diffraction across the Al K edge, where the aluminum scattering factor changes dramatically. By combining conventional synchrotron powder diffraction data with those collected at energies near the X-ray absorption edge, aluminum is highlighted. In this way, the different distributions of aluminum in two FER-type zeolites with identical chemical compositions but different catalytic properties could be determined unambiguously. The results are consistent with previous studies, but quantitative. This approach constitutes a major advance in our fundamental understanding of the relationship between zeolite structure and catalytic activity.

Anomalous X-Ray Scattering and Extended X-Ray Absorption Fine Structure Study of the Local Structure of CrFeCoNiMox (x = 0.11, 0.18, and 0.23) High-Entropy Alloys

Anomalous x-ray scattering (AXS) and extended x-ray absorption fine structure (EXAFS) were used to determine the local structure of Mo in CrFeCoNiMox (x = 0.11, 0.18, and 0.23), a high-entropy alloy with a face-centered cubic (FCC) lattice. No superlattice peaks were observed down to the 10–4 intensity level. This observation along with the nearly constant decrease of the FCC diffraction peaks above the Mo K absorption edge suggests that Mo atoms have no preferred site occupancy in the FCC lattice. Modeling of the EXAFS data suggests a local chemical order in CrFeCoNiMox, where in Mo-rich samples (e.g., x = 0.23), Mo atoms are preferably surrounded by lighter atoms, such as Cr.

Likelihood-based estimation of substructure content from single-wavelength anomalous diffraction (SAD) intensity data.

SAD phasing can be challenging when the signal-to-noise ratio is low. In such cases, having an accurate estimate of the substructure content can determine whether or not the substructure of anomalous scatterer positions can successfully be determined. Here, a likelihood-based target function is proposed to accurately estimate the strength of the anomalous scattering contribution directly from the measured intensities, determining a complex correlation parameter relating the Bijvoet mates as a function of resolution. This gives a novel measure of the intrinsic anomalous signal. The SAD likelihood target function also accounts for correlated errors in the measurement of intensities from Bijvoet mates, which can arise from the effects of radiation damage. When the anomalous signal is assumed to come primarily from a substructure comprising one anomalous scatterer with a known value of f'' and when the protein composition of the crystal is estimated correctly, the refined complex correlation parameters can be interpreted in terms of the atomic content of the primary anomalous scatterer before the substructure is known. The maximum-likelihood estimation of substructure content was tested on a curated database of 357 SAD cases with useful anomalous signal. The prior estimates of substructure content are highly correlated to the content determined by phasing calculations, with a correlation coefficient (on a log-log basis) of 0.72.

I Spy Transits and Pulsations: Empirical Variability in White Dwarfs Using Gaia and the Zwicky Transient Facility

Abstract We present a novel method to detect variable astrophysical objects and transient phenomena using anomalous excess scatter in repeated measurements from public catalogs of Gaia DR2 and Zwicky Transient Facility (ZTF) DR3 photometry. We first provide a generalized, all-sky proxy for variability using only Gaia DR2 photometry, calibrated to white dwarf stars. To ensure more robust candidate detection, we further employ a method combining Gaia with ZTF photometry and alerts. To demonstrate its efficacy, we apply this latter technique to a sample of roughly 12,100 white dwarfs within 200 pc centered on the ZZ Ceti instability strip, where hydrogen-atmosphere white dwarfs are known to pulsate. By inspecting the top 1% of the samples ranked by these methods, we demonstrate that both the Gaia-only and ZTF-informed techniques are highly effective at identifying known and new variable white dwarfs, which we verify using follow-up, high-speed photometry. We confirm variability in all 33 out of 33 (100%) observed white dwarfs within our top 1% highest-ranked candidates, both inside and outside the ZZ Ceti instability strip. In addition to dozens of new pulsating white dwarfs, we also identify five white dwarfs highly likely to show transiting planetary debris; if confirmed, these systems would more than triple the number of white dwarfs known to host transiting debris.

Direct Observation of the Xenon Physisorption Process in Mesopores by Combining In Situ Anomalous Small-Angle X-ray Scattering and X-ray Absorption Spectroscopy.

The morphology and structural changes of confined matter are still far from being understood. This report deals with the development of a novel in situ method based on the combination of anomalous small-angle X-ray scattering (ASAXS) and X-ray absorption near edge structure (XANES) spectroscopy to directly probe the evolution of the xenon adsorbate phase in mesoporous silicon during gas adsorption at 165 K. The interface area and size evolution of the confined xenon phase were determined via ASAXS demonstrating that filling and emptying the pores follow two distinct mechanisms. The mass density of the confined xenon was found to decrease prior to pore emptying. XANES analyses showed that Xe exists in two different states when confined in mesopores. This combination of methods provides a smart new tool for the study of nanoconfined matter for catalysis, gas, and energy storage applications.

ASAXS study of the influence of sulfidation conditions and organic additives on sulfide slabs multiscale organization

One of the ways to improve the activity of the sulfide catalysts is to increase the quantity of molybdenum up to contents greater than 15 wt%. For such high Mo contents, the distribution of MoS2 particles is suspected to play an important role in the catalytic activity. A complete description of the active phase is thus required and implies measuring i) the size and stacking distribution of the isolated slabs, ii) the proportion of Mo involved in aggregates or individual slabs, iii) the size of the aggregates. These steps are essential to deeply explain the intrinsic activity of the catalysts. To address this challenge, Anomalous Small-Angle X-ray Scattering (ASAXS) analyses have been performed on different sets of catalysts, prepared with various organic additives and activated either by a gas sulfidation (1 bar, 350 °C,15%H2S/H2) or by real industrial liquid sulfidation (30 bar, 350 °C, H2/gas oil/DMDS). Furthermore, the spent catalysts were also characterized after HDS catalytic test on a real feedstock. The aim of this study was not to elucidate in detail the chemical mechanisms involved when using additives or different sulfidation conditions, but rather to better understand the impact of the microstructural organization on catalytic performances and demonstrate the potential of the ASAXS technique to give new insights on the multi-scale organization of the molybdenum active phase. We thus demonstrate that ASAXS allows to obtain a more detailed description of the slabs compared to TEM and, simultaneously, to identify and quantify the aggregation state of the particles which occurs on high loaded catalysts. The role of the additives is clearly highlighted after liquid sulfidation, as we demonstrate the dispersive effect of triethylene glycol and thioglycolic acid and to a lower extent of citric acid. The slab length and stacking are decreased, as well as the aggregate amount and size. The analysis of the spent catalysts have also revealed the significant evolution of the active phase under HDS reaction conditions. Among other parameters, the aggregate amount appears as a relevant descriptor since a correlation is found with the intrinsic catalytic performances, which suggests an issue of active sites accessibility.