Anomalous X-ray Research Articles

Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction.

Anomalous X-ray diffraction (AXD) and neutron diffraction can be used to crystallographically distinguish between metals of similar electron density. Despite the use of AXD for structural characterization in mixed metal clusters, there are no benchmark studies evaluating the accuracy of AXD toward assessing elemental occupancy in molecules with comparisons with what is determined via neutron diffraction. We collected resonant diffraction data on several homo and heterometallic clusters and refined their anomalous scattering components to determine metal site occupancies. Theoretical resonant scattering terms for Fe0, Co0, and Zn0 were compared against experimental values, revealing theoretical values are ill-suited to serve as references for occupancy determination. The cluster featuring distinct cation and anion metal compositions [CoCp2*][(tbsL)Fe3(μ3-NAr)] was used to assess the accuracy of different f' references for occupancy determination (f'theoretical ± 15-17%; f'experimental ± 10%). This methodology was applied toward calculating the occupancy of three different clusters: (tbsL)Fe2Zn(py) (6), (tbsL)Fe2Zn(μ3-NAr)(py) (7), and [CoCp*2][(tbsL)Fe2Zn(μ3-NAr)] (8). The first two clusters maintain 100% Fe/Zn site isolation, whereas 8 showed metal mixing within the sites. The large crystal size of 8 enabled collection of neutron diffraction data which was compared against the results found with AXD. The ability of AXD to replicate the metal occupancies as determined by neutron diffraction supports the AXD occupancy methodology developed herein. Furthermore, the advantages innate to AXD (e.g., smaller crystal sizes, shorter collection times, and greater availability of synchrotron resources) versus neutron diffraction further support the need for its development as a standard technique.

Evolution of strengthening precipitates in Al-4.0Zn-1.8Mg-1.2Cu (at.%) alloy with high Zn/Mg ratio during artificial aging

Evolution of strengthening precipitates, including their types, sizes, volume fraction, and chemical compositions in Al-4.0Zn-1.8Mg-1.2Cu (at.%) alloy during artificial aging, were investigated using anomalous small-angle X-ray scattering (ASAXS), three-dimensional atom probe techniques (APT), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and density functional theory (DFT) calculation. Upon aging, Cu-containing clusters merge with adjacent clusters to form larger clusters, which then act as nucleation sites for GPη' zones. As aging proceeds, GPη' zones grow up to η'I metastable phase with seven atomic layers on {111}Al planes, and this process is controlled by diffusion of Mg atoms. Cu atoms have a low diffusion rate and do not participate into the growth of precipitates within the first 60mins of aging. As aging time increases, Cu atoms enter the η'I metastable phase, leading to a significant increase in Cu content and (Zn+Cu)/Mg ratio; η'I metastable phase grow, and after exceeding about 7nm, gradually transform into the η'II metastable phase with ten atomic layers by adding three new atomic layers at one side. GPη' zones, η'I metastable phase and η'II metastable phase have symmetric interface structures. The precipitation sequence during aging to peak state can be summarized as: atomic clusters → GPη' zones → η'I metastable phase → η'II metastable phase.

Fine structural analysis of calcium–niobium–gallium garnet (CNGG) by single-crystal anomalous X-ray scattering

Single-crystal anomalous X-ray scattering (AXS) experiments were conducted to investigate the cation distribution of calcium–niobium–gallium garnet (CNGG). AXS measurements suggested an ordered distribution of Nb at the octahedral site, and further structural refinement allowed us to obtain the structural formula Ca3Nb1.703(0) Ga3.162(2)O12. Ca was only located in the dodecahedral site, while Ga was distributed in the octa- and tetrahedral sites. The tetrahedral site had a significant number of vacancies at a ratio of one vacancy per unit cell, and the Nb/Ga occupation ratio at the octahedral site results in non-stoichiometric chemical composition of CNGG and its unique broad absorption wavelength.The findings of this study can contribute to device fabrication, property optimization, and quality control processes related to CNGG.

Multipolar Electromagnetic Emission of Newborn Magnetars

It is generally recognized that the electromagnetic multipolar emission from magnetars can be used to explain radiation from soft gamma repeaters or anomalous X-ray pulsars, but they have little impact on the spin-down of magnetars. We here present an analytical solution for the neutron star multipolar electromagnetic fields and their associated expected luminosities. We find that for newborn millisecond magnetars, the spin-down luminosity from higher multipolar components can match or even exceed that from the dipole component. Such high-intensity radiation will undoubtedly affect related astrophysical phenomena at the birth of a magnetar. We show that the spin-down luminosity from multipoles can well explain the majority of gamma-ray burst (GRB) afterglows, from the plateau starting at several hundred seconds until the normal decay phase lasting for many years. The fitted magnetar parameters for GRB afterglows are all typical values, with spins in the millisecond range and magnetic field strengths on the order of 1014–1015 G. Our results, in turn, provide support for the hypothesis that GRBs originate from the birth of magnetars with a period of a few milliseconds, thus deepening our understanding of the complex magnetic field structure and the equation of state of magnetars.

Distribution of Eu and Er in Ca9RE(PO4)7 phosphors analyzed by anomalous X-ray scattering

The structures of Ca9Eu(PO4)7 and Ca9Er(PO4)7 phosphors were analyzed using single-crystal X-ray diffraction. Most Eu ions reside at the medium-sized M1 and M2 sites, with a small amount occupying the M5 site. In contrast, the smaller Er ions favor the smallest M5 site. This study also demonstrates the use of anomalous X-ray scattering measurements at the Er LIII and Er LIII-edges. The energy dependencies observed in the scattering factors for Ca9Eu(PO4)7 and Ca9Er(PO4)7 confirmed the preferred distribution of Eu and Er. Because this anomalous X-ray scattering method leverages the unique anomalous dispersion terms of each element, this advanced technique, coupled with a synchrotron radiation source, is suggested to be a powerful method for distinguishing near-neighbor rare-earth elements in solid-state phosphors.

Long-term evolutionary links between the isolated neutron star populations

ABSTRACT We have investigated the evolutionary connections of the isolated neutron star (NS) populations including radio pulsars (RPs), anomalous X-ray pulsars (AXPs), soft gamma repeaters (SGRs), dim isolated NSs (XDINs), ‘high-magnetic field’ RPs (‘HBRPs’), central compact objects (CCOs), rotating radio transients (RRATs), and long-period pulsars (LPPs) in the fallback disc model. The model can reproduce these NS families as a natural outcome of different initial conditions (initial period, disc mass, and dipole moment, μ) with a continuous μ distribution in the $\sim 10^{27} - 5 \times 10^{30}$ G cm$^3$ range. Results of our simulations can be summarized as follows: (1) A fraction of ‘HBRPs’ with relatively high μ evolve into the persistent AXP/SGR properties, and subsequently become LPPs. (2) Persistent AXP/SGRs do not have evolutionary links with CCOs, XDINs, and RRATs. (3) For a wide range of μ, most RRATs evolve passing through RP or ‘HBRP’ properties during their early evolutionary phases. (4) A fraction of RRATs which have the highest estimated birth rate seem to be the progenitors of XDINs. (5) LPPs, whose existence was predicted by the fallback disc model, are the sources evolving in the late stage of evolution before the discs become inactive. These results provide concrete support to the ideas proposing evolutionary connections between the NS families to account for the ‘birth rate problem’, the discrepancy between the cumulative birth rate estimated for these systems and the core-collapse supernova rate.

Quantitative localisation of titanium in the framework of titanium silicalite-1 using anomalous X-ray powder diffraction

One of the biggest obstacles to developing better zeolite-based catalysts is the lack of methods for quantitatively locating light heteroatoms on the T-sites in zeolites. Titanium silicalite-1 (TS-1) is a Ti-bearing zeolite-type catalyst commonly used in partial oxidation reactions with H2O2, such as aromatic hydroxylation and olefin epoxidation. The reaction mechanism is controlled by the configuration of titanium sites replacing silicon in the zeolite framework, but these sites remain unknown, hindering a fundamental understanding of the reaction. This study quantitatively determines heteroatoms within the zeolite-type framework using anomalous X-ray powder diffraction (AXRD) and the changes in the titanium X-ray scattering factor near the Ti K-edge (4.96 keV). Two TS-1 samples, each with approximately 2 Ti atoms per unit cell, were examined. Half of the titanium atoms are primarily split between sites T3 and T9, with the remainder dispersed among various T-sites within both MFI-type frameworks. One structure showed significant non-framework titanium in the micropores of a more distorted lattice. In both samples, isolated titanium atoms were more prevalent than dinuclear species, which could only potentially arise at site T9, but with a significant energy penalty and were not detected.

Unusual spinel in the “Verde Prato” serpentinized peridotite

A petrographic study of “Verde Prato” (trade name of an ophiolitic serpentinised peridotite quarried in Tuscany) revealed, next to a relict Cr-spinel, another opaque ore mineral apparently containing ca.17 wt% SiO2. In order to unveil the origin of this anomalous composition, detailed SEM-EDS, μ-Raman spectroscopy and X-ray μ-diffraction investigations were undertaken, which provided useful but somehow contrasting indications. Therefore, in order to definitely unveil the nature of the unusual opaque mineral, a specific TEM study was undertaken. This showed the presence of submicroscopic euhedral Mn-Cr-Fe-spinels in a matrix of a 7 Å layer-silicate (Al-lizardite). Interesting, all the submicroscopic spinel grains were found to share the same crystallographic orientation, suggesting an origin from a single, larger, former crystal. This unusual type of alteration of the mantle spinel probably occurred on the ocean floor during the pervasive polyphase process of hydrothermal peridotite serpentinization. Overall, by mapping the different serpentinite microstructures and compositions, a polyphase serpentinization history consisting of at least eight different cycles has been suggested. Moreover, the spinel composition indicates that the alteration was accompanied by Mn-metasomatism, made possible by the close proximity of Mn-rich hydrothermal vents, such as “black smokers”.

Quantifying the Hydration-Dependent Dynamics of Cu Migration and Activity in Zeolite Omega for the Partial Oxidation of Methane.

Copper-exchanged zeolite omega (Cu-omega) is a potent material for the selective conversion of methane-to-methanol (MtM) via the oxygen looping approach. However, its performance exhibits substantial variation depending on the operational conditions. Under an isothermal temperature regime, Cu-omega demonstrates subdued activity below 230 °C, but experiences a remarkable increase in activity at 290 °C. Applying a high-temperature activation protocol at 450 °C causes a rapid deactivation of the material. This behavioral divergence is investigated by combining reactivity studies, neutron diffraction and in situ high-resolution anomalous X-ray powder diffraction (HR-AXRPD), as well as electron paramagnetic resonance spectroscopy, to reveal that the migration of Cu throughout the framework is the primary cause of these behaviors, which in turn is predominantly governed by the degree of hydration of the system. This work suggests that control over the Cu migration throughout the zeolite framework may be harnessed to significantly increase the activity of Cu-omega by generating more active sites for the MtM conversion. These results underscore the power of in situ HR-AXRPD for unraveling the behavior of materials under reaction conditions and suggest that a re-evaluation of Cu-zeolites priorly deemed inactive for the MtM conversion across a broader range of conditions and looping protocols may be warranted.

Deep-learning map segmentation for protein X-ray crystallographic structure determination.

When solving a structure of a protein from single-wavelength anomalous diffraction X-ray data, the initial phases obtained by phasing from an anomalously scattering substructure usually need to be improved by an iterated electron-density modification. In this manuscript, the use of convolutional neural networks (CNNs) for segmentation of the initial experimental phasing electron-density maps is proposed. The results reported demonstrate that a CNN with U-net architecture, trained on several thousands of electron-density maps generated mainly using X-ray data from the Protein Data Bank in a supervised learning, can improve current density-modification methods.

Enhancing atomic ordering, magnetic and transport properties of Mn2VGa Heusler alloy thin films toward negatively spin-polarized charge injection

Magnetic materials with negative spin polarization have attracted attention for their potential to increase the design freedom of spintronic devices. This study investigated the effects of off-stoichiometry on the atomic ordering, microstructure, and magneto-transport properties in Mn2+xV1−xGa (x = −0.2, 0, +0.2, +0.4) Heusler alloy films, which are predicted to have large negative spin polarization derived from a pseudo band gap in the majority spin channel. The Mn2+xV1−xGa films epitaxially grown on MgO(001) substrates exhibits variations of B2 and L21 order with the Mn concentration. A high-quality L21 ordered film was achieved in the Mn-rich composition (x = +0.2) with B2 and L21 order parameters of 0.97 and 0.86, respectively, and a saturation magnetization of 1.4 μB/f.u., which agrees with the Slater-Pauling rule. Scanning transmission electron microscopy observations showed that B2 and L21 phases coexist in Mn-poor and stoichiometric films, while the L21 phase is dominant in the Mn-rich film with small amounts of Mn–V and Mn–Ga disorders, as revealed by laboratory and anomalous X-ray diffraction. Combined first-principles calculations and anisotropic magnetoresistance analysis confirms that the addition of excess Mn preserves the high spin polarization by suppressing the formation of detrimental antisites of V atoms occupying Mn sites. Therefore, the Mn-rich composition is promising for negatively spin-polarized charge injection in Mn2VGa-based spintronic applications.

Oxidation-induced surface stress on texture development of thin films: The (001) FePt case

Residual stress is an inevitable characteristic in all kinds of thin film materials. The incorporation of stress and physical properties may also be of importance as a stress-driven functional characteristics, particularly in the context of engineering texture and anisotropies in magnetic thin film materials. A mechanism explaining the (001) preferred orientation in the rapidly annealed FePt thin films is proposed on the basis of the experimental study of the oxidation-induced surface stress measurements. By adopting a grazing incidence anomalous x-ray diffraction based on synchrotron radiation, the depth-resolved stress distribution of the FePt films was investigated. A substantial in-plane tensile stress induced by surface oxidation was observed in the FePt thin films. The oxidation layer, with an appropriate thickness, maintains the accumulated tensile stress, thereby inducing the (001) preferred orientation in FePt. The surface stress relaxation was observed in the FePt films with the processes lacking oxygen or in a poor vacuum condition.

Anomalous X-ray pulse responses in MAPbBr3 single crystal-based detectors

Organic-inorganic perovskite single crystals (SCs) are considered promising semiconductors for high-sensitivity X-ray detectors because of their strong X-ray interaction, low-temperature processability, and excellent properties such as long diffusion length, low defect density, and long carrier lifetime. However, the specific pulse response of MAPbBr3 SC-based X-ray detectors frequently exhibits a tail and over/undershoots at several conditions, which degrades the X-ray image quality; however, no detailed analysis of these characteristics has been reported thus far. For high-resolution X-ray imaging, it is necessary to obtain an ideal pulse response that is free of tails and over/undershoots. In this study, we investigated the specific X-ray responses of solution-grown MAPbBr3 SC-based X-ray detectors under various externally applied voltages. Based on the study on charge carrier dynamics, we analyzed the origin of the tail and over/undershoots in X-ray pulse response shapes. We theoretically verified that the unideal pulse response in perovskite SC-based X-ray detectors is attributed to the defect states inherent in perovskite SCs.

Formation of a zirconium oxide crystal nucleus in the initial nucleation stage in aluminosilicate glass investigated by X-ray multiscale analysis

Understanding the nucleation mechanism in glass is crucial for the development of new glass-ceramic materials. Herein, we report the structure of a commercially important glass-ceramic ZrO2-doped lithium aluminosilicate system during its initial nucleation stage. We conducted an X-ray multiscale analysis, and this analysis was used to observe the structure from the atomic to the nanometer scale by using diffraction, small-angle scattering, absorption, and anomalous scattering techniques. The inherent phase separation between the Zr-rich and Zr-poor regions in the pristine glass was enhanced by thermal treatment without changing the spatial geometry at the nanoscale. Element-specific pair distribution function analysis using anomalous X-ray scattering data showed the formation of a liquid ZrO2-like local structural motif and edge sharing between the ZrOx polyhedra and (Si/Al)O4 tetrahedra during the initial nucleation stage. Furthermore, the local structure of the Zr4+ ions resembled a cubic or tetragonal ZrO2 crystalline phase and formed after 2 h of annealing the pristine glass. Therefore, the Zr-centric periodic structure formed in the early stage of nucleation was potentially the initial crystal nucleus for the Zr-doped lithium aluminosilicate glass-ceramic.

Unraveling pH-Dependent Changes in Adsorption Structure of Uranyl on Alumina (012).

Mitigating uranium transport in groundwater is imperative for ensuring access to clean water across the globe. Here, in situ resonant anomalous X-ray reflectivity is used to investigate the adsorption of uranyl on alumina (012) in acidic aqueous solutions, representing typical UVI concentrations of contaminated water near mining sites. The analyses reveal that UVI adsorbs at two distinct heights of 2.4-3.2 and 5-5.3 Å from the surface terminal oxygens. The former is interpreted as the mixture of inner-sphere and outer-sphere complexes that adsorb closest to the surface. The latter is interpreted as an outer-sphere complex that shares one equatorial H2O with the terminal surface oxygen. With increasing pH, we observe an increasing prevalence of these outer-sphere complexes, indicating the enhanced role of the hydrogen bond that stabilizes adsorbed uranyl species. The presented work provides a molecular-scale understanding of sorption of uranyl on Al-based-oxide surfaces that has implications for environmental chemistry and materials science.

Quantitative Determination of Metal Ion Adsorption on Cellulose Nanocrystals Surfaces.

Nanocellulose is a bio-based material that holds significant potential in the field of water purification. Of particular interest is their potential use as a key sorbent material for the removal of metal ions from solution. However, the structure of metal ions adsorbed onto cellulose surfaces is not well understood. The focus of this work is to determine quantitatively the three-dimensional distribution of metal ions of different valencies surrounding negatively charged carboxylate functionalized cellulose nanocrystals (CNCs) using anomalous small-angle X-ray scattering (ASAXS). These distributions can affect the water and ionic permeability in these materials. The data show that increasing the carboxylate density on the surface of the CNCs from 740 to 1100 mmol/kg changed the nature of the structure of the adsorbed ions from a monolayer into a multilayer structure. The monolayer was modeled as a Stern layer around the CNC nanoparticles, whereas the multilayer structure was modeled as a diffuse layer on top of the Stern layer around the nanoparticles. Within the Stern layer, the maximum ion density increases from 1680 to 4350 mmol of Rb+/(kg of CNC) with the increase in the carboxylate density on the surface of the nanoparticles. Additionally, the data show that CNCs can leverage multiple mechanisms, such as electrostatic attraction and the chaotropic effect, to adsorb ions of different valencies. By understanding the spatial organization of the adsorbed metal ions, the design of cellulose-based sorbents can be further optimized to improve the uptake capacity and selectivity in separation applications.

Uranyl uptake into metal-organic frameworks: a detailed X-ray structural analysis.

Metal-organic frameworks (MOF) are a subclass of porous framework materials that have been used for a wide variety of applications in sensing, catalysis, and remediation. Among these myriad applications is their remarkable ability to capture substances in a variety of environments ranging from benign to extreme. Among the most common and problematic substances found throughout the world's oceans and water supplies is [UO2]2+, a common mobile ion of uranium, which is found both naturally and as a result of anthropogenic activities, leading to problematic environmental contamination. While some MOFs possess high capability for the uptake of [UO2]2+, many more of the thousands of MOFs and their modifications that have been produced over the years have yet to be studied for their ability to uptake [UO2]2+. However, studying the thousands of MOFs and their modifications presents an incredibly difficult task. As such, a way to narrow down the numbers seems imperative. Herein, we evaluate the binding behaviors as well as identify the specific binding sites of [UO2]2+ incorporated into six different Zr MOFs to elucidate specific features that improve [UO2]2+ uptake. In doing so, we also present a method for the determination and verification of these binding sites by Anomalous wide-angle X-ray scattering, X-ray fluorescence, and X-ray absorption spectroscopy. This research not only presents a way for future research into the uptake of [UO2]2+ into MOFs to be conducted but also a means to evaluate MOFs more generally for the uptake of other compounds to be applied for environmental remediation and improvement of ecosystems globally.

Polarized X-Rays Detected from the Anomalous X-Ray Pulsar 1E 2259+586

Anomalous X-ray pulsars (AXPs) and soft gamma-ray repeaters (SGRs) are believed to be associated with magnetars, which have extremely strong magnetic fields. Recently, with the operation of the Imaging X-ray Polarimetry Explorer (IXPE), the polarization information of two AXPs and one SGR have been investigated. In this work, we report the observational results of the fourth magnetar, 1E 2259+586, with IXPE, and perform a joint analysis with observations from Neutron Star Interior Composition Explorer. We find that the emission from 1E 2259+586 is linearly polarized, with a polarization degree (5.3% ± 1.3%) and a polarization angle −77° ± 7° in the 2–8 keV energy range. Additionally, both the polarization degree and polarization angle exhibit variability with the pulse phase, and there is a hint of anticorrelation between the polarization degree and the flux, which is similar to AXP 1RXS J170849.0-400910. The phase-dependent polarization angle displays a sinusoidal profile and can be well fitted with the rotating vector model, indicating that the magnetic dipole field dominated the magnetic structure of the pulsar, and the variation in the polarization angle was modulated by the pulsar’s rotation.

Revealing the evolution of local structures in the formation process of alkaline earth metal cation-containing zeolites from glasses.

Alkaline earth metal cations are ubiquitously present in natural zeolites but less exploited in synthetic zeolites due to their low solubility in water, and hence it remains elusive how they contribute to zeolite formation. Herein, harmotome, a PHI-type zeolite with Ba2+, is readily synthesized from a Ba-containing aluminosilicate glass. This glass-to-zeolite transformation process, in particular the structure-regulating role of Ba2+, is investigated by anomalous X-ray scattering and high-energy X-ray total scattering techniques. The results demonstrate that the steady Ba2+-aluminosilicate interactions not only help prevent the precipitation of barium species under alkaline synthetic conditions, but also dictate the local structures with distinct interatomic distances between the Ba2+ and the surrounding aluminosilicate species throughout the transformation process, which lead to the successful formation of harmotome without detectable impurities. This study highlights the usefulness of the comprehensive X-ray scattering techniques in revealing the formation scheme of the zeolites containing specific metal species. In addition, a promising alternative approach to design and synthesize zeolites with unique compositions and topologies by using well-crafted glasses with suitable metal cation dopants is demonstrated.

No Dispersed Single Radio Pulses Detected in Archival Parkes Pulsar Observations Targeting Supernova Remnants and Anomalous X-Ray Pulsars

Four supernova remnants and four anomalous X-ray pulsars were previously observed with the Parkes telescope in a campaign to detect pulsed radio emission from associated neutron stars. No signals were detected in the original searches of these data. I have reprocessed the data with the more recently developed HEIMDALL and FETCH software packages, which are optimized for single-pulse detection and classification. In this new analysis, no astrophysical pulses were detected having a signal-to-noise ratio above 7 from any of the targets at dispersion measures ranging from 0 to 104 pc cm−3. I include calculated fluence limits on single radio pulses from these targets.