Search

In the present work, we have investigated the structural response of transition metal double perovskite oxide Nd 2 CoFeO 6 under pressure by XRD and Raman spectroscopic measurements. From XRD data, we have observed a pressure-induced structural transition from the orthorhombic phase to the monoclinic phase at about 14.8 GPa. An anomalous increase in compressibility at a much lower pressure (∼ 1.1 GPa) is seen where no structural transition occurs. At about the same pressure, a sudden drop in the slope of the Raman shift is observed. Further investigation at low temperatures reveals that the B 1 g Raman mode is strongly affected by magnetic interactions. Additional high-pressure Raman experiments with the application of a magnetic field have indicated that the mentioned anomaly around 1.1 GPa can be explained by a high-spin to low-spin transition of Co 3 + . [ABSTRACT FROM AUTHOR]

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4 GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits. [ABSTRACT FROM AUTHOR]

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4 GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits. [ABSTRACT FROM AUTHOR]

Strain engineering using ion beams is a current topic of research interest in semiconductor materials. Synchrotron-based high-resolution x-ray diffraction has been utilized for strain-depth analysis in GaAs irradiated with 300 keV Ar and 4H-SiC and GaAs irradiated with 100 MeV Ag ions. The direct displacement-related defect formation, anticipated from the elastic energy loss of Ar ions, can well explain the irradiation-induced strain depth profiles. The maximum strain in GaAs is evaluated to be 0.88% after Ar irradiation. The unique energy loss depth profile of 100 MeV Ag (swift heavy ions; SHIs) and resistance of pristine 4H-SiC and GaAs to form amorphous/highly disordered ion tracks by ionization energy loss of monatomic ions allow us to examine strain buildup due to the concentrated displacement damage by the elastic energy loss near the end of ion range (∼ 12 μ m). Interestingly, for the case of SHIs, the strain-depth evolution requires consideration of recovery by ionization energy loss component in addition to the elastic displacement damage. For GaAs, strain builds up throughout the ion range, and the maximum strain increases and then saturates at 0.37% above an ion fluence of 3 × 10 13 Ag/cm 2. For 4H-SiC, the maximum strain reaches 4.6% and then starts to recover for fluences above 1 × 10 13 Ag/cm 2. Finally, the contribution of irradiation defects and the purely mechanical contribution to the total strain have been considered to understand the response of different compounds to ion irradiation. [ABSTRACT FROM AUTHOR]

Temperature dependent bonding behavior plays a significant role in deciding properties of high temperature ceramics like boron carbide. However, few studies to date have addressed the physical properties of this class of materials with respect to their temperature dependent bonding nature. In addition, materials with the flexibility to accommodate variations in interatomic bonding and lattice vibrations over a wide range of temperatures are less known. In this work, temperature dependent structural analyses of carbon-rich boron carbide microflakes using in situ powder x-ray diffraction techniques (up to 1000 °C) supported by transmission electron microscopy measurements reveal that while most bonds in the rhombohedral structure increase in length with temperature; there is no change in certain bond lengths. However, there is an unusual decrease in length (∼1.03%) of the inter-cluster –C–(central boron)BC–C– without any polyhedral redistribution. This is accompanied by an increase in lattice vibrations without significant alteration to the crystal structure over the wide temperature range studied. Temperature dependent micro-Raman experiments further confirmed the above observations. The above bonding behavior could be directly correlated to the trends in reported results of high temperature conductivity via the model of hole hopping through specific atomic positions of the rhombohedral framework, thus opening the scope to investigate structure–property relationships in high temperature functional materials. [ABSTRACT FROM AUTHOR]

Grazing incidence x-ray diffraction reveals that conventional post-deposition-annealed ZrO2 and in situ crystallized (by local epitaxy) ZrO2 thin films (<15 nm) have different internal strain states. A comparison between single- and two-step grown films enables the diverse strain components to be discretely identified. In particular, thickness-dependent intrinsic growth strain is unevenly distributed within the film according to the Volmer–Weber growth. Furthermore, extrinsic thermal strain, locally present in the annealed seed layer, does not spread over the in situ crystallized upper main layer of the two-step film. Post-deposition annealing of the two-step film renders the strain state identical to the single-step films by imposing thermal strain on the in situ crystallized main layer. Local strains created by diffused aluminum and yttrium dopants are also examined. Since each stress factor plays a vital role in the phase formation and electrical behaviors of ZrO2 and other fluorite-structure films, this method will pave the way for understanding the film's internal strain distribution and accompanying performance engineering. [ABSTRACT FROM AUTHOR]

In this work, pure and S–N/WO3 (1%–7%) nanoparticles (NPs) have been developed for the degradation of MB dye. Optical properties, vibrational analysis, morphology, structural analysis, and photocatalytic activity of the samples have been evaluated using a variety of characterization techniques, including UV–vis, PL, FTIR, SEM, and x-ray diffraction (XRD). The XRD patterns showed that the stability of the orthorhombic phase of WO3 was affected by the concentrations of S and N. In SEM, nanospheres with an average size of 80 nm of NPs have been observed. The PL results showed that the e−, h+ recombination rate for the S–N7%/WO3 sample was the lowest. The degradation of MB dye has also been investigated in order to investigate the photocatalytic performance. Remarkably, S–N7%/WO3 shows the best results, with a maximum degradation of 90% in 120 min. The stability of the improved catalyst was tested using recycling and trapping studies. S–N7%/WO3 catalyst's exceptional photocatalytic activity highlights its potential use in wastewater treatment. This study will be helpful for manufacturing innovation. [ABSTRACT FROM AUTHOR]

We investigated the spectrum of density fluctuations of a liquid crystal, CB7CB, in two different orientations by using high-resolution inelastic x-ray scattering. Our analysis, based on Bayesian principles, revealed that high-frequency collective excitations propagate through this mesoscale-ordered sample in a peculiar manner that lies somewhere between those observed in liquids and crystalline systems. Interestingly, when we probed longer length scales, a more pronounced solid-like response emerged. This was mainly characterized by anomalously sharp inelastic excitations and the onset of shear mode propagation. Comparison with previous x-ray diffraction results suggests a correlation between the observed behavior and the mesogen arrangement. [ABSTRACT FROM AUTHOR]

Position-dependent three-dimensional reciprocal space mapping (RSM) by nanobeam x-ray diffraction (nanoXRD) was performed to reveal the strain fields produced around individual threading dislocations (TDs) in GaN substrates. The distribution and Burgers vector of TDs for the nanoXRD measurements were confirmed by prerequisite analysis of multi-photon excited photoluminescence and etch pit methods. The present results demonstrated that the nanoXRD can identify change in the lattice plane structure for all types of TDs, i.e., edge-, screw-, and mixed TDs with the Burgers vector of b = 1a, 1c and 1m + 1c. Strain tensor components related to edge and/or screw components of the TDs analyzed from the three-dimensional RSM data showed a nearly symmetrical strained region centered on the TD positions, which were in good agreements with simulation results based on the isotropic elastic theory using a particular Burgers vector. The present method is beneficial in that it allows non-destructive analysis of screw components of TDs that tend to contribute to leakage characteristics and are not routinely accessible by conventional structural analysis. These results indicate that nanoXRD could be a powerful way to reveal three-dimensional strain fields associated with arbitrary types of TDs in semiconductor materials, such as GaN and SiC. [ABSTRACT FROM AUTHOR]

Ethane ( C 2 H 6 ) is anticipated to be the most stable compound within the carbon–hydrogen system under the 100 GPa pressure range. Nevertheless, the properties of ethane under pressure are still poorly documented. Here, we present a comprehensive study of the structural and vibrational properties of C 2 H 6 in a diamond anvil cell at pressures up to 150 GPa. To obtain detailed data, ethane single-crystal was grown in a helium pressure-transmitting medium. Utilizing single-crystal x-ray diffraction, the distortion mechanism between the tetragonal and monoclinic phases, occurring over the 3.2–5.2 GPa pressure range, is disclosed. Subsequently, no phase transition is observed up to 150 GPa. The accurately measured compression curve is compared to various computational approximations. The vibrational modes measured by Raman spectroscopy and infrared absorption are well identified, and their evolution is well reproduced by ab initio calculations. In particular, an unusual anticrossing phenomenon occurs near 40 GPa between a rocking and a stretching mode, likely attributable to intermolecular interactions through hydrogen bonding. [ABSTRACT FROM AUTHOR]

In this study, phase transitions (structural and magnetic) and associated magnetocaloric properties of stoichiometric MnCoGe have been investigated as a function of annealing pressure. Metastable phases were generated by annealing at 800 ° C followed by rapid cooling under pressures up to 6.0 GPa. The x-ray diffraction results reveal that the crystal cell volume of the metastable phases continuously decreases with increasing thermal processing pressure, leading to a decrease in the structural transition temperature. The magnetic and structural transitions merge and form a first-order magnetostructural transition between the ferromagnetic orthorhombic and paramagnetic hexagonal phases over a broad temperature range (>80 K) spanning room temperature, yielding considerable magnetic entropy changes. These findings demonstrate the utility of thermal processing under high pressure, i.e., high-pressure annealing, to control the magnetostructural transitions and associated magnetocaloric properties of MnCoGe without altering its chemical composition. [ABSTRACT FROM AUTHOR]

Ion hydration plays a crucial role in numerous fundamental processes. Various spectroscopic methods are employed to investigate the slowing down of hydration bond dynamics in the proximity of both anions and cations. To date, most of these studies have primarily focused on the properties of binary systems. However, in comparison to ion–water binary systems, ternary systems that involve ions, water, and organic matter are more prevalent in nature and provide more realistic insights into biological processes. This study focuses on ion hydration in water and alcohol mixture using terahertz spectroscopy and x-ray diffraction (XRD). The results reveal a distinct behavior depending on the type of alcohol used. Specifically, the presence of both methanol and ethanol results in the disappearance of absorption peaks associated with NaCl hydrate at low temperatures. In contrast, tert-butanol does not exhibit such an effect, and isopropanol demonstrates a more complex response. By combining these terahertz spectroscopic findings with low-temperature XRD data, we gain insights into the formation, or lack thereof, of NaCl · 2H2O hydrate crystals. Crucially, our observations suggest a dominant correlation between the polarity of the alcohol molecules and its impact on the Na+ hydration. Strongly polar alcohols preferentially solvating the Na+ ion lead to the failure of hydrate formation, while weakly polar alcohols do not have this effect. [ABSTRACT FROM AUTHOR]

GaOx devices have been extensively explored for applications such as power devices and solar blind detectors, based on their wide bandgap. In this study, we investigated the synaptic properties of the amorphous gallium oxide (a-GaOx)- based memristor with a W/WOx/a-GaOx/ITO structure, in which a-GaOx are deposited by RF magnetic sputtering at ambient temperature. The structure and components of a-GaOx are characterized by XRD, XPS, SEM, and EDS. The electrical test indicates that W/WOx/a-GaOx is ohmic due to the thin WOx layer with a high concentration of oxygen vacancies. Consequently, the synaptic characteristics of the W/WOx/a-GaOx/ITO memristor depend on both the a-GaOx layer itself and the a-GaOx/ITO junction. The fitting results indicate that the a-GaOx/ITO junction is Schottky with unidirectional conductive properties. However, the elevated defect density results in a larger current for the reverse-biased a-GaOx/ITO junction. Moreover, adjusting the thickness of a-GaOx allows the device to achieve almost symmetrical forward and reverse currents. We have successfully observed typical synaptic characteristics in W/WOx/a-GaOx/ITO when stimulated by consecutive spike signals. Clearly, through careful design considerations regarding the structure and parameters, we have realized superior synaptic performance in a-GaOx-based memristors. This achievement shows that amorphous GaOx has great potential applications in neuromorphic computation chips for artificial intelligence or the Internet of Things in the future. [ABSTRACT FROM AUTHOR]

The present study focuses on the oxygen (O)-ion implantation-induced structural and electronic modifications in the single crystals of strontium-titanate (s-STO) using synchrotron-based x-ray diffraction (XRD), x-ray photoemission spectroscopy (XPS), and resonant x-ray photoemission spectroscopy. The crystallinity of the epitaxially aligned phases of s-STO is confirmed through XRD. This direct evidence of heavy ion implantation is supported by the Monte Carlo-based simulation of stopping and range of ions in matter/transport of ions in matter. XPS at different core levels is performed to detect the exact oxidation state of Ti ions in s-STO. The dominance of Ti3+ over Ti4+ upon oxygen implantation suggests the disorder in the perovskite material, primarily in the form of oxygen vacancies (VO). The confirmation of VO is explicitly shown by the enhancement in the spectral area of the assigned peak in the O 1s XPS. Resonant photoemission spectroscopy measurements were performed by varying photon energy from 32 to 46 eV to understand the nature of the valence band electronic structure of s-STO. The resonance in the different hybridized states of s-STO is confirmed by the spectral features of constant initial state plots. There is a correlation between the defective state of Ti and the oxygen-deficient state. The transformation from SrTiO3 to SrTiO2.5, partially or completely, is essentially required to underline any modification in the electronic properties of s-STO. s-STO is in a mixed state of an ionic conductor and an electronic conductor. This study outlines the creation of VO due to O-ion implantation and investigates the changes in the electronic structures of s-STO. [ABSTRACT FROM AUTHOR]

Drug discovery relies on efficient identification of small-molecule leads and their interactions with macromolecular targets. However, understanding how chemotypes impact mechanistically important conformational states often remains secondary among high-throughput discovery methods. Here, we present a conformational discovery pipeline integrating time-resolved, high-throughput small-angle X-ray scattering (TR-HT-SAXS) and classic fragment screening applied to allosteric states of the mitochondrial import oxidoreductase apoptosis-inducing factor (AIF). By monitoring oxidized and X-ray-reduced AIF states, TR-HT-SAXS leverages structure and kinetics to generate a multidimensional screening dataset that identifies fragment chemotypes allosterically stimulating AIF dimerization. Fragment-induced dimerization rates, quantified with time-resolved SAXS similarity analysis (kVR), capture structure-activity relationships (SAR) across the top-ranked 4-aminoquinoline chemotype. Crystallized AIF-aminoquinoline complexes validate TR-SAXS-guided SAR, supporting this conformational chemotype for optimization. AIF-aminoquinoline structures and mutational analysis reveal active site F482 as an underappreciated allosteric stabilizer of AIF dimerization. This conformational discovery pipeline illustrates TR-HT-SAXS as an effective technology for targeting chemical leads to important macromolecular states.

The molecular foundations of epidermal cell wall mechanics are critical for understanding structure-function relationships of primary cell walls in plants and facilitating the design of bioinspired materials. To uncover the molecular mechanisms regulating the high extensibility and strength of the cell wall, the onion epidermal wall is stretched uniaxially to various strains and cell wall structures from mesoscale to atomic scale are characterized. Upon longitudinal stretching to high strain, epidermal walls contract in the transverse direction, resulting in a reduced area. Atomic force microscopy shows that cellulose microfibrils exhibit orientation-dependent rearrangements at high strains: longitudinal microfibrils are straightened out and become highly ordered, while transverse microfibrils curve and kink. Small-angle X-ray scattering detects a 7.4 nm spacing aligned along the stretch direction at high strain, which is attributed to distances between individual cellulose microfibrils. Furthermore, wide-angle X-ray scattering reveals a widening of (004) lattice spacing and contraction of (200) lattice spacing in longitudinally aligned cellulose microfibrils at high strain, which implies longitudinal stretching of the cellulose crystal. These findings provide molecular insights into the ability of the wall to bear additional load after yielding: the aggregation of longitudinal microfibrils impedes sliding and enables further stretching of the cellulose to bear increased loads.

Grazing-incidence x-ray diffraction (GIXRD) is a scattering technique that allows one to characterize the structure of fluid interfaces down to the molecular scale, including the measurement of surface tension and interface roughness. However, the corresponding standard data analysis at nonzero wave numbers has been criticized as to be inconclusive because the scattering intensity is polluted by the unavoidable scattering from the bulk. Here, we overcome this ambiguity by proposing a physically consistent model of the bulk contribution based on a minimal set of assumptions of experimental relevance. To this end, we derive an explicit integral expression for the background scattering, which can be determined numerically from the static structure factors of the coexisting bulk phases as independent input. Concerning the interpretation of GIXRD data inferred from computer simulations, we extend the model to account also for the finite sizes of the bulk phases, which are unavoidable in simulations. The corresponding leading-order correction beyond the dominant contribution to the scattered intensity is revealed by asymptotic analysis, which is characterized by the competition between the linear system size and the x-ray penetration depth in the case of simulations. Specifically, we have calculated the expected GIXRD intensity for scattering at the planar liquid–vapor interface of Lennard-Jones fluids with truncated pair interactions via extensive, high-precision computer simulations. The reported data cover interfacial and bulk properties of fluid states along the whole liquid–vapor coexistence line. A sensitivity analysis shows that our findings are robust with respect to the detailed definition of the mean interface position. We conclude that previous claims of an enhanced surface tension at mesoscopic scales are amenable to unambiguous tests via scattering experiments. [ABSTRACT FROM AUTHOR]

We report an enhanced magnetoelectric (ME) effect in spin–phonon coupled single-phase La1−xSmxYFe2O6 (0 ≤ x ≤ 1). The structural, electric, magnetic, and ME properties have been investigated to establish their interplay leading to magnetoelectricity. X-ray diffraction study suggests the facilitation of the P21nm phase (double perovskite lattice arrangements) formation and improved structural order due to the substitution of Sm in the lattice. Antiferromagnetic (AFM) transition ∼700 K along with a spin-reorientation transition around room temperature (RT) and below is observed in the thermomagnetic curve. The indication of short range ordering in the magnetization data in the form of a non-Griffiths-like phase (nGP) is observed. The short range ordering could be minimized along with consequent improvement in AFM ordering, due to Sm substitution. An enhanced (∼31% with respect to x = 0) RT first-order ME coupling coefficient ∼0.59 mV cm−1 Oe−1 in x = 0.75 composition is observed. The findings reported here open the door to exercise spin-reorientation transition in the spin–phonon coupled double perovskites for spintronic device applications. [ABSTRACT FROM AUTHOR]

We report an enhanced magnetoelectric (ME) effect in spin–phonon coupled single-phase La1−xSmxYFe2O6 (0 ≤ x ≤ 1). The structural, electric, magnetic, and ME properties have been investigated to establish their interplay leading to magnetoelectricity. X-ray diffraction study suggests the facilitation of the P21nm phase (double perovskite lattice arrangements) formation and improved structural order due to the substitution of Sm in the lattice. Antiferromagnetic (AFM) transition ∼700 K along with a spin-reorientation transition around room temperature (RT) and below is observed in the thermomagnetic curve. The indication of short range ordering in the magnetization data in the form of a non-Griffiths-like phase (nGP) is observed. The short range ordering could be minimized along with consequent improvement in AFM ordering, due to Sm substitution. An enhanced (∼31% with respect to x = 0) RT first-order ME coupling coefficient ∼0.59 mV cm−1 Oe−1 in x = 0.75 composition is observed. The findings reported here open the door to exercise spin-reorientation transition in the spin–phonon coupled double perovskites for spintronic device applications. [ABSTRACT FROM AUTHOR]

In this report, the high-temperature transport properties of (Dy1−xCax)(Zr0.2Hf0.2Sn0.2Ti0.2Ge0.2)O7 pyrochlore oxides with x = 0, 0.05, and 0.1 are studied in dry and humid air. The phase composition and crystal structure were determined by using x-ray and neutron diffraction. The addition of calcium to the structure caused an increase in the concentration of oxygen vacancies, indicating an ionic charge compensation mechanism. Electrical studies allowed us to determine the total electrical conductivity as a function of the synthesis atmosphere and pH2O. The electrical conductivity turned out to be at the level of ∼10−3 S/cm at 800 °C, and only a slight effect of the presence of protonic defects in the structure on the total electrical conductivity was observed. In general, the samples had a low electrical conductivity with a relatively high activation energy of conduction. [ABSTRACT FROM AUTHOR]

Nanowires (NWs) composed of 2,4-bis[(4-diethylamino)-2-hydroxyphenyl] squaraine were prepared by evaporation-induced self-assembly (EISA). NWs were ∼560 nm wide (aspect ratios: 10–90). X-ray diffraction analysis indicated polymorphism (monoclinic/triclinic). Optical data reported the triclinic phase with energetic disorder. Given the favorable alignment of the Au work function and squaraine HOMO energy, symmetric, unipolar metal–insulator–metal devices were formed by the EISA of NW meshes on inter-digitated Au electrodes. Room temperature DC I–V characteristics displayed hysteretic I–V loops, indicating memristive behavior. At low bias, data indicated Ohmic transport with carrier extraction facilitated by thermionic emission. At high biases, devices exhibited space-charge-limited conduction in the presence of shallow traps. At 77 K, data indicated Ohmic transport at low bias with carrier extraction by thermionic emission while, at high biases, trap-limited space-charge-limited conduction in the presence of traps distributed in energy, with carrier extraction by Fowler–Nordheim tunneling, was observed. The I–V hysteresis was eliminated at 77 K and attenuated by fast scan rates at room temperature, suggesting that carrier trapping/de-trapping underpinned the hysteresis. In impedance measurements, the device response fitted a Randles equivalent circuit indicating purely electronic conduction. By applying voltage waveforms, I–V hysteresis and analog resistive switching (memristive) functionality were observed. Device conductance could be increased sweep by sweep, giving conductance tuning through distinct states, with wait time- or voltage-erase options, consistent with trap filling/emptying effects. Repeated erase–write–read of multiple distinct states over many voltage cycles during continuous use in air was demonstrated. Finally, synaptic functions, e.g., pulse-dependent plasticity, and short- to long-term memory transition, were successfully emulated. [ABSTRACT FROM AUTHOR]

The effect of the GaAsP strain-compensating layer on type-II GaAs1−xSbx/InyGa1−yAs was investigated. GaAsSb/InGaAs multiple quantum wells (MQWs) without and with GaAsP strain-compensating layers were grown by molecular beam epitaxy. Increasing Sb or In compositions can extend photoluminescence (PL) emission at longer wavelength along with the highly induced compressive strain in the QWs. The power-dependent PL measured at low temperature reveals the type-II band characteristics of the GaAs1−xSbx/InyGa1−yAs system. A detailed analysis of the experimental data reveals that the GaAsP layers compensate the compressive strain of GaAsSb/InGaAs. The type-II QWs with GaAsP layers, (8 nm) GaAs0.84Sb0.16/(2.5 nm) In0.3Ga0.7As/(10 nm) GaAs0.85P0.15, emits PL at ∼1.1 μm, up to 210 K, while the PL of those strained sample without GaAsP vanishes at lower temperature. In view of the described sample, x-ray diffraction (XRD) analysis along with the simulation shows the validity of the procedure, resulting in nearly matched parameters of QW thicknesses and material compositions—(8.9 nm) GaAs0.835Sb0.165/(2.3 nm) In0.3Ga0.7As/(10.3 nm) GaAs0.85P0.15, with those of the designed QW. The thicknesses of QW from the TEM image, (8.6 nm) GaAsSb/(3.1 nm) InGaAs/(10.1 nm) GaAsP, agree well with the XRD results. [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.

Tungstates and molybdates possessing the scheelite- and wolframite-type (if present) structures hold a significant functional value. Their high-pressure phase diagrams are very complicated and controversial, and even some parts have not been characterized yet. In this study, we investigate the sequence of pressure driven structural phase transitions up to 100 GPa in these tungstate and molybdate families via first-principles structure predictions. Based on our structural predictions, it is possible for isostructural tungstates and molybdates to exhibit a phase transition sequence that is either similar or identical. Examples of these compounds are CaWO4, CaMoO4, and CdMoO4, in addition to EuWO4 and EuMoO4. However, the phase transition sequences of some tungstates and molybdates, especially those with different divalent cations, display noteworthy variations, revealing the intricate influence of ionic radii and electronic properties on crystal configurations. To obtain a deeper understanding of the high-pressure phase transition behavior of tungstates and molybdates, we analyze the high-pressure phase diagrams of MgWO4, SrWO4, and CaMoO4, representative examples of wolframite-type tungstate, scheelite-type tungstate, and scheelite-type molybdate, respectively, using x-ray powder diffraction. Our x-ray diffraction experiments and structure predictions consistently verify that the orthorhombic Cmca phase is a high-pressure phase of SrWO4. Structural configurations and mechanical properties of these predicted structures are discussed, and electronic properties are given. This study could have important implications for the fields of seismology and geophysics, as well as the utilization of these materials in various capacities, such as photocatalysts, photoanodes, and phosphors. [ABSTRACT FROM AUTHOR]

Silicene, a 2D hexagonal structure of silicon, has shown great promise for next-generation advanced electronic devices due to recent progress. However, one major obstacle to its application and integration into devices is its strong tendency of rapid oxidation in an ambient environment. Enhancing the chemical inertness by means of chemical modification without comprising its unique structure and properties is vital. Here, we report the fabrication of hydrogenated silicene grown on polycrystalline Ag films by means of plasma-enhanced chemical-vapor deposition (PECVD) with proper hydrogen dilution. Our Raman spectroscopy and x-ray diffraction results show the existence of typical monolayer and few-layer silicene. The x-ray photoelectron spectroscopy demonstrates its oxidation resistance after a few minutes of air exposure in a class 100 clean room. We propose that PECVD silicene can be an alternative to molecular-beam-epitaxy silicene for potential low-cost and large-area silicene applications. [ABSTRACT FROM AUTHOR]

Here, we present a new approach for obtaining radial distribution functions (RDF) from the electron diffraction data using a regularized weighted sine least-squares spectral analysis. It allows for explicitly transferring the measured experimental uncertainties in the reduced molecular scattering function to the produced RDF. We provide a numerical demonstration, discuss the uncertainties and correlations in the RDFs, and suggest a regularization parameter choice criterion. The approach is also applicable for other diffraction data, e.g., for x-ray or neutron diffraction of liquid samples. [ABSTRACT FROM AUTHOR]

1-propanol/water mixtures over the whole composition range (0 < XV ≤ 1; XV is the 1-propanol volume fraction) are shown to be structurally and dynamically heterogeneous. By combining structural (x-ray diffraction), thermodynamic (differential scanning calorimetry) and dynamical probes (dielectric spectroscopy) we construct the pertinent phase diagram. It consists of liquid 1-propanol, liquid water, hexagonal ice and different hydrates, the latter sharing the same lattice. The phase diagram can be discussed in terms of four regimes, all having in common a droplet arrangement of the minority component. When water droplets are strongly confined by 1-propanol (regime I, 0.92 < XV ≤ 1; "soft" confinement), water is unable to crystallize. It has dynamics reminiscent to the ultra-viscous water phase known as high-density liquid (HDL). When water droplets are moderately confined (regime II, 0.75 < XV ≤ 0.92) water can crystallize via homogeneous nucleation. Strikingly, the homogeneous nucleation temperature is at 205 K, well within "no-man's land." The result is in line with earlier reports that soft confinement is the key to enter into the "no-man's land". When 1-propanol is the minority component (regimes III and IV), the structure and the dynamics are dominated by the 1-propanol/water interface with the formation of hydrates. The corresponding dynamical features suggest a link between hydrate formation and the two metastable phases of ultra-viscous water, HDL and low-density liquid. [ABSTRACT FROM AUTHOR]

In situ temperature-dependent crystal structure of lead-free ferroelectric perovskite Ba0.798Ca0.202Zr0.006Ti0.994O3 single crystal was characterized using x-ray diffraction from 170 to 380 K. Three phases were identified at different temperatures of 170, 220, and 298 K, revealing rhombohedral (R3m), orthorhombic (Pmm2), and tetragonal (P4mm) crystal structures, respectively. The change in the bond length and its distortion are reported for both AO12 and BO6 polyhedrons, allowing for the estimation of the spontaneous polarization. The Debye–Waller factor is reported as a function of temperature for A and B-sites. Density-functional theory calculations on the tetragonal phase were performed to obtain information on the distribution of the Ca ions, the local atomic displacements, and the ideal value of the spontaneous polarization of a defect-free crystal at 0 K. We find that Ca prefers to arrange in columnar 2D plates oriented along the tetragonal axis. The Ca ions avoid being next neighbors of Zr; however, the specific arrangement of Ca has only a minor impact on the spontaneous polarization. [ABSTRACT FROM AUTHOR]

Transition-metal and rare-earth borides are of considerable interest due to their electronic, mechanical, and magnetic properties as well as their structural stability under extreme conditions. Here, we report on a series of high-pressure Raman and x-ray diffraction experiments on the cubic rare-earth hexaboride EuB6 to an ultrahigh pressure of 187 GPa in a diamond anvil cell. In EuB6, divalent europium ions occupy the corners of the cubic structure, which encloses a rigid boron-bonded cage. So far, no structural phase transitions have been reported, while the nanoindentation studies indicate amorphization in nanoscale shear bands during plastic deformation. Our x-ray diffraction studies have revealed that the ambient cubic phase of EuB6 shows broadening and splitting of diffraction peaks starting at 72 GPa and the broadening continuing to 187 GPa. The high-pressure phase is recovered on decompression, and the Raman spectroscopy of the recovered sample from 187 GPa shows a downward frequency shift and broadening of T2g, Eg, and A1g modes of boron octahedron. The density functional theory simulations of EuB6 at 100 GPa have identified five possible lowest energy crystal structures. The experimental x-ray diffraction data at high pressures is compared with the theoretical predictions and the role of structural distortions induced by shear stresses is also discussed. [ABSTRACT FROM AUTHOR]

The axon-initial-segment (AIS) of mature neurons contains microtubule (MT) fascicles (linear bundles) implicated as retrograde diffusion barriers in the retention of MT-associated protein (MAP) tau inside axons. Tau dysfunction and leakage outside of the axon is associated with neurodegeneration. We report on the structure of steady-state MT bundles in varying concentrations of Mg2+ or Ca2+ divalent cations in mixtures containing αβ-tubulin, full-length tau, and GTP at 37 °C in a physiological buffer. A concentration-time kinetic phase diagram generated by synchrotron SAXS reveals a wide-spacing MT bundle phase (Bws), a transient intermediate MT bundle phase (Bint), and a tubulin ring phase. SAXS with TEM of plastic-embedded samples provides evidence of a viscoelastic intervening network (IN) of complexes of tubulin oligomers and tau stabilizing MT bundles. In this model, αβ-tubulin oligomers in the IN are crosslinked by taus MT binding repeats, which also link αβ-tubulin oligomers to αβ-tubulin within the MT lattice. The model challenges whether the cross-bridging of MTs is attributed entirely to MAPs. Tubulin-tau complexes in the IN or bound to isolated MTs are potential sites for enzymatic modification of tau, promoting nucleation and growth of tau fibrils in tauopathies.

Abstract: The crystal structure and bonding environment of K2Ca(CO3)2 bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus, $${K}_{0}=46.9$$ K 0 = 46.9 GPa with an imposed value of $${K}_{0}^{\prime}= 4$$ K 0 ′ = 4 for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along the c-axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinic C2/m structure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields $${V}_{0}=322.2$$ V 0 = 322.2  Å3$$,$$ , $${K}_{0}=24.8$$ K 0 = 24.8 GPa and $${K}_{0}^{\prime}=4.0$$ K 0 ′ = 4.0 using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of the C2/m phase involves interlayer displacement and twisting of the [CO3] units, and an increase in coordination number of the K+ ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO3] bonding environments within the structure.

Electron bifurcation (BF) is an evolutionarily ancient energy coupling mechanism in anaerobes, whose associated enzymatic machinery remains enigmatic. In BF-flavoenzymes, a chemically high-potential electron forms in a thermodynamically favorable fashion by simultaneously dropping the potential of a second electron before its donation to physiological acceptors. The cryo-EM and spectroscopic analyses of the BF-enzyme Fix/EtfABCX from Thermotoga maritima suggest that the BF-site contains a special flavin-adenine dinucleotide and, upon its reduction with NADH, a low-potential electron transfers to ferredoxin and a high-potential electron reduces menaquinone. The transfer of energy from high-energy intermediates must be carefully orchestrated conformationally to avoid equilibration. Herein, anaerobic size exclusion-coupled small-angle X-ray scattering (SEC-SAXS) shows that the Fix/EtfAB heterodimer subcomplex, which houses BF- and electron transfer (ET)-flavins, exists in a conformational equilibrium of compacted and extended states between flavin-binding domains, the abundance of which is impacted by reduction and NAD(H) binding. The conformations identify dynamics associated with the T. maritima enzyme and also recapitulate states identified in static structures of homologous BF-flavoenzymes. Reduction of Fix/EtfABCX's flavins alone is insufficient to elicit domain movements conducive to ET but requires a structural "trigger" induced by NAD(H) binding. Models show that Fix/EtfABCX's superdimer exists in a combination of states with respect to its BF-subcomplexes, suggesting a cooperative mechanism between supermonomers for optimizing catalysis. The correlation of conformational states with pathway steps suggests a structural means with which Fix/EtfABCX may progress through its catalytic cycle. Collectively, these observations provide a structural framework for tracing Fix/EtfABCX's catalysis.