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DOE OSTI2020

Factors Defining the Intercalation Electrochemistry of CaFe 2 O 4 -Type Manganese Oxides

Oxides with the CaFe 2 O 4 -type structure have been predicted as being suitable hosts for reactions of intercalation of light cations such as Li and Mg because of their favorable cationic diffusion. Although Li has been shown to intercalate into the Mn 2 O 4 variant, the key structure property correlations determining function are not fully ascertained. This basic information is needed before attempting the intercalation of divalent cations, which face comparably higher migration barriers. For this purpose, here the electrode function of CaFe 2 O 4 -type Li 0.8 Mn 2 O 4 was compared for materials made by a direct high-pressure route or through cation exchange from NaMn 2 O 4 . X-ray diffraction and absorption spectroscopy revealed that, despite having largely the same bulk structure, the presence of surface defects blocked Li + transfer in Li 0.8 Mn 2 O 4 made at high pressure. These defects were not present in the cation-exchanged material, which resulted in highly reversible Li intercalation with very fast kinetics in micrometric crystals. Delithiated electrodes from the cation-exchange synthesis were subsequently reduced in an ionic liquid electrolyte containing Mg 2+ . The process induced topotactic changes in the bulk, strongly suggesting the existence of intercalation, but it is accompanied by severe reactivity with the electrolyte that impedes reversibility. This study uncovers that defects affect the fundamentals of cation intercalation in this novel class of materials. The ability of the cation-exchanged material to conduct fast reactions with Li is consistent with calculated activation energy barriers and creates promise for their use as Mg hosts, provided that novel electrolytes enhanced stability at high potential can be realized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Scanning tunneling microscopy study of the antiferromagnetic topological insulator MnBi 2 Se 4

Topological insulators with intrinsic magnetic ordering such as MnBi 2 Se 4 have been predicted to host many exotic topological phenomena including dissipationless edge states and magnetoelectric effects. Here we use scanning tunneling microscopy to study the surface of MnBi 2 Se 4 epitaxial thin films. Large scale topographic images show steps between van der Waals layers and screw dislocations. While we find the Se-termination predominant on the surface, areas attributed to Bi-termination are found at the edges of small islands in as-grown films, or in larger areas upon removal of surface capping. Here, we compare these terminations through an analysis of step heights, atomic resolution images and tunneling spectroscopy. Tunneling spectra on the Se-termination reveals semiconducting behavior, with an apparent bandgap of >0.18eV that depends on the tip height. In contrast, tunneling spectra of the Bi-termination appears gapless, which could be an indication of dangling bond states on the surface. In both cases, a hexagonal 3.9Å lattice is observed that is consistent with the expected crystal structure.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Quantum critical point followed by Kondo-like behavior due to Cu substitution in the itinerant antiferromagnet La 2 ⁢(Cu 𝑥 ⁢Ni 1−𝑥 ) 7

La 2 ⁢Ni 7 is an itinerant magnetic system with a small ordered moment of ∼ 0.1⁢µ 𝐵 /Ni and a series of antiferromagnetic (AFM) transitions at 𝑇 1 = 61.0K, 𝑇 2 = 56.5K, and 𝑇 3 = 42.2K. 𝑀 ⁡(𝐻), and 𝜌 ⁡(𝐻) isotherms as well as constant field 𝑀⁡ (𝑇) and 𝜌 ⁡(𝑇) measurements on single-crystalline samples manifest a complex, anisotropic 𝐻−𝑇 phase diagram with multiple phase lines. Here, in this study, we present the growth and characterization of single crystals of the La 2 ⁢(Cu 𝑥 ⁢Ni 1−𝑥 ) 7 series for 0 ≤ 𝑥 ≤ 0.181. We measured powder x-ray diffraction and composition, as well as anisotropic temperature- and field-dependent resistivity, temperature- and field-dependent magnetization, and temperature-dependent heat capacity on these single crystals. Using the measured data we infer a transition temperature-composition (𝑇−𝑥) phase diagram for this system to study the evolution of the AFM ordering upon Cu substitution. For 0 ≤ 𝑥 ≤ 0.097, the system remains magnetically ordered at base temperature with 𝑥 ≤ 0.012, showing signs of multiple AFM ordering temperatures. For the higher substitution levels 0.125 ≤ 𝑥 ≤ 0.181, there are no signatures of magnetic ordering, but anomalous features in resistance and heat capacity data are observed which are consistent with the Kondo effect in this system. The intermediate 𝑥 = 0.105 sample lies between the magnetic ordered and the Kondo regime and is in the vicinity of the AFM quantum critical point (QCP). Thus, La 2⁢ (Cu 𝑥 ⁢Ni 1−𝑥 ) 7 is an example of a small moment system that can be tuned through a QCP. Given these data combined with the fact that the La 2⁢ Ni 7 structure has kagomelike, Ni sublattices running perpendicular to the crystallographic 𝑐 axis, and a predicted 3⁢𝑑-electron flat band that contributes to the density of states near the Fermi energy, La 2 ⁢(Cu 𝑥 ⁢Ni 1−𝑥 ) 7 becomes a promising system to host and study exotic physics.

Das, Atreyee [Ames Laboratory, and Iowa State Univ↗
DOE OSTI2021

Ionizing photon interactions modulate the optical properties of crystals with femtosecond scale temporal resolution

In this work, we continue our study of a new method for the detection of ionizing radiation with the potential for a dramatic improvement in coincidence time resolution (CTR) for time-of-flight positron emission tomography (ToF-PET) using the modulation of a material's optical properties instead of the scintillation mechanism. Our previous work has shown that for non-scintillation materials such as bismuth silicon oxide (BSO) and cadmium telluride (CdTe), their refractive index can be modulated by annihilation photon interactions. Additionally, the ultrafast nature of this process however remains unexplored. The ionizing radiation-induced charge carriers alter the local band structure in these materials, thus changing the complex refractive index. This mechanism is routinely used at the linac coherent light source (LCLS) facility of the SLAC National Accelerator Laboratory to measure x-ray pulse arrival times with femtosecond scale resolution for photon energies between 0.5 and 10 keV. The method described here follows that example by using a frequency chirped visible continuum pulse to provide a monotonic wavelength-to-time mapping by which one can measure the time-dependent refractive index modulation. In addition, we describe an interference-based measurement setup that allows for significantly improved sensitivity while preserving a timing precision of approximately 10 fs (σ) when measuring the arrival time of below 10 keV x-ray pulses with yttrium aluminum garnet (YAG) crystal. The method is presented in the context of ToF-PET application with further discussions on the potential CTR achievable if a similar detection concept is adopted for detecting 511 keV photons. Semi-empirical analysis indicates that the predicted CTR achievable is on the order of 1 ps (FWHM).

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Influence of Protection Layers on Thermal Stability of Nitride Thin Films

Nitrides are commonly studied for their properties relevant to numerous coating applications, and have been recently used to synthesize newly predicted materials in thin film form. However, thermodynamic stability of such nitride materials is difficult to experimentally evaluate, due to limited thermal budget of thin films. Here we show that thermal stability of nitride films can be extended using protection layers. Specifically, we find that zirconium nitride (ZrN) thin films are stable up to at least 1200°C annealing temperature in N2 atmosphere, if aluminum nitride (AlN) diffusion barriers and capping layers are used. X-ray diffraction (XRD) measurements show the expected thermodynamically stable rocksalt structure of ZrN, and scanning electron microscopy (SEM) confirms compact microstructure of these ZrN films. Without such protection layers, transient bixbyite Zr2ON2 phase and high-temperature ZrSi2 phase are observed after annealing by XRD, SEM, and auger electron spectroscopy (AES), due to side reaction with native surface oxide (ZrOx) and substrate (Si) respectively. These results demonstrate that protection layers are beneficial to increase the thermal budget of nitride thin films, for evaluating thermodynamic stability of new nitride materials, for capturing transient metastable phases during crystallization, and for using functional nitride coatings in extreme environments.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Selecting XFEL single-particle snapshots by geometric machine learning

A promising new route for structural biology is single-particle imaging with an X-ray Free-Electron Laser (XFEL). This method has the advantage that the samples do not require crystallization and can be examined at room temperature. However, high-resolution structures can only be obtained from a sufficiently large number of diffraction patterns of individual molecules, so-called single particles. Here, we present a method that allows for efficient identification of single particles in very large XFEL datasets, operates at low signal levels, and is tolerant to background. This method uses supervised Geometric Machine Learning (GML) to extract low-dimensional feature vectors from a training dataset, fuse test datasets into the feature space of training datasets, and separate the data into binary distributions of “single particles” and “non-single particles.” As a proof of principle, we tested simulated and experimental datasets of the Coliphage PR772 virus. We created a training dataset and classified three types of test datasets: First, a noise-free simulated test dataset, which gave near perfect separation. Second, simulated test datasets that were modified to reflect different levels of photon counts and background noise. These modified datasets were used to quantify the predictive limits of our approach. Third, an experimental dataset collected at the Stanford Linear Accelerator Center. The single-particle identification for this experimental dataset was compared with previously published results and it was found that GML covers a wide photon-count range, outperforming other single-particle identification methods. Moreover, a major advantage of GML is its ability to retrieve single particles in the presence of structural variability.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Controlling the Self-Assembly of DNA Origami Octahedra via Manipulation of Inter-Vertex Interactions

Recent studies have demonstrated novel strategies for the organization of nanomaterials into three-dimensional (3D) ordered arrays with prescribed lattice symmetries using DNA-based self-assembly strategies. In one approach, the nanomaterial is sequestered into DNA origami frames or “material voxels” and then coordinated into ordered arrays based on the voxel geometry and the corresponding directional interactions based on its valency. While the lattice symmetry is defined by the valency of the bonds, a larger-scale morphological development is affected by assembly processes and differences in energies of anisotropic bonds. To facilely model this assembly process, we investigate the self-assembly behavior of hard particles with six interacting vertices via theory and Monte Carlo simulations and exploration of corresponding experimental systems. We demonstrate that assemblies with different 3D crystalline morphologies, but the same lattice symmetry can be formed depending on the relative strength of vertex-to-vertex interactions in orthogonal directions. We observed three distinct assembly morphologies for such systems: cube-like, sheet-like, and cylinder-like. A simple analytical theory inspired by well-established ideas in the areas of protein crystallization, based on calculating the second virial coefficient of patchy hard spheres, captures the simulation results and thus represents a straightforward means of modeling this self-assembly process. To complement the theory and simulations, experimental studies were performed to investigate the assembly of octahedral DNA origami frames with varying binding energies at their vertices. In conclusion, x-ray scattering confirms the robustness of the formed nanoscale lattices for different binding energies, while both optical and electron microscopy imaging validated the theoretical predictions on the dependence of the distinct morphologies of assembled state on the interaction strengths in the three orthogonal directions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enhancing stability, magnetic anisotropy, and coercivity of manganese aluminum: Machine learning, ab initio , and micromagnetic modeling

The binary manganese aluminum (MnAl) alloy with L⁢1 0 crystal structure is a promising rare earth (RE) element-free permanent magnetic material because of its exceptional magnetic properties. However, experimentally synthesizing it in a stable bulk form is extremely challenging. Here, in this study, an alternative method of stabilizing the material, a pathway for experimental synthesis and validation, is proposed and theoretically verified. This is done by partially substituting Mn and Al sites with Fe and Ni and identifying its enhanced phase stability, saturation magnetization density, magnetic anisotropy, and coercivity from density functional theory (DFT), machine learning (ML) crystal graph convolution neural network (CGCNN), and micro-magnetic modeling. When considering a fixed 50% Ni, the magnetic anisotropy increases with the increasing Fe content but decreases the formation energy. The calculated formation energies, elastic constants, and phonon frequencies demonstrate that the binary and quaternary compositions are stable. Most importantly, in 50% Fe and Ni-substituted-equiatomic phase, magnetic anisotropy constants and saturation magnetization density increase by 56% and 23% as compared to the MnAl. Further, the coercivity of the equiatomic phase predicted with micro-magnetic modeling is higher by 17% than the parent compound.

Bhandari, Churna [Ames National Laboratory, and Io↗
DOE OSTI2025

When more data hurts: Optimizing data coverage while mitigating diversity-induced underfitting in an ultrafast machine-learned potential

Machine-learned interatomic potentials (MLIPs) are becoming an essential tool in materials modeling. However, optimizing the generation of training data used to parametrize the MLIPs remains a significant challenge. This is because MLIPs can fail when encountering local environments too different from those present in the training data. The difficulty of determining a priori the environments that will be encountered during molecular dynamics simulation necessitates diverse, high-quality training data. Here, this study investigates how training data diversity affects the performance of MLIPs using the Ultra-Fast force field (UF 3 ) to model amorphous silicon nitride. We employ expert and autonomously generated data to create the training data and fit four force field variants to subsets of the data. Our findings reveal a critical balance in training data diversity: insufficient diversity hinders generalization, while excessive diversity can exceed the MLIP's learning capacity, reducing simulation accuracy. Specifically, we found that the UF 3 variant trained on a subset of the training data, in which nitrogen-rich structures were removed, offered vastly better prediction and simulation accuracy than any other variant. By comparing these UF 3 variants, we highlight the nuanced requirements for creating accurate MLIPs, emphasizing the importance of application-specific training data to achieve optimal performance in modeling complex material behaviors.

ab initio molecular dynamics↗
NASA NTRS2004

External and Internal Reconnection in Two Filament-Carrying Magnetic-Cavity Solar Eruptions

We observe two near-limb solar filament eruptions, one of 2000 February 26 and the other of 2002 January 4. For both we use 195 A Fe XII images from the Extreme-Ultraviolet Imaging Telescope (EIT) and magnetograms from the Michelson Doppler Imager (MDI), both of which are on the Solar and Heliospheric Observatory (SOHO). For the earlier event we also use soft X-ray telescope (SXT), hard X-ray telescope (HXT), and Bragg Crystal Spectrometer (BCS) data from the Yohkoh satellite, and hard X-ray data from the BATSE experiment on the Compton Gamma Ra.v Observatory (CGRO). Both events occur in quadrupolar magnetic regions, and both have coronal features that we infer belong to the same magnetic cavity structures as the filaments. In both cases, the cavity and filament first rise slowly at approx.10 km/s prior to eruption and then accelerate to approx.100 km/s during the eruption, although the slow-rise movement for the higher altitude cavity elements is clearer in the later event. We estimate that both filaments and both cavities contain masses of approx.10(exp 14)-10(exp 15) and approx.10(exp 15)-10(exp 16) g, respectively. We consider whether two specific magnetic reconnection-based models for eruption onset, the "tether cutting" and the "breakout" models, are consistent with our observations. In the earlier event, soft X-rays from SXT show an intensity increase during the 12 minute interval over which fast eruption begins, which is consistent with tether- cutting-model predictions. Substantial hard X-rays, however, do not occur until after fast eruption is underway, and so this is a constraint the tether-cutting model must satisfy. During the same 12 minute interval over which fast eruption begins, there are brightenings and topological changes in the corona indicative of high-altitude reconnection early in the eruption, and this is consistent with breakout predictions. In both eruptions, the state of the overlying loops at the time of onset of the fast-rise phase of the corresponding filament can be compared with expectations from the breakout model, thereby setting constraints that the breakout model must meet. Our findings are consistent with both runaway tether-cutting-type reconnection and fast breakout-type reconnection, occurring early in the fast phase of the February eruption and with both types of reconnection being important in unleashing the explosion, but we are not able to say which, if either, type of reconnection actually triggered the fast phase. In any case, we have found specific constraints that either model, or any other model, must satisfy if correct.

Sterling, Alphonse C.↗
DOE OSTI2020

Two-Dimensional Uranyl Borates: From Conventional to Extreme Synthetic Conditions: Two-Dimensional Uranyl Borates: From Conventional to Extreme Synthetic Conditions

A systematic investigation of uranyl borates under different synthetic conditions resulted in five new 2D compounds, namely, (H 3 O)[(UO 2 )(BO 3 )], Li[(UO 2 )(BO 3 )] · (H 2 O), α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ], β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 . (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O) were obtained from hydrothermal reactions at 220 °C using the same mineralizer. Both materials possess the uranophane sheet topology with different symmetry of the unit cells. In the structure of (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O), UO 7 pentagonal bipyramids share edges and vertexes with four BO 3 planar triangles. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] are polytypes. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was synthesized from a high-temperature solid-state reaction under ambient pressure; whereas β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was obtained from a high-temperature/high-pressure (HT/HP) reaction. Both structures have an identical anion topology, but β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] crystallizes in space group with higher symmetry. In K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 , which was obtained from a hydrothermal reaction, UO 7 polyhedra share vertexes and edges with two independent BO 3 triangles, forming the most complex uranyl borate layers among all five compounds. The different synthetic routes, novel topologies, thermal behavior and Raman spectra are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Data-driven analysis of neutron diffraction line profiles: application to plastically deformed Ta

Abstract Non-destructive evaluation of plastically deformed metals, particularly diffraction line profile analysis (DLPA), is valuable both to estimate dislocation densities and arrangements and to validate microstructure-aware constitutive models. To date, the interpretation of whole line diffraction profiles relies on the use of semi-analytical models such as the extended convolutional multiple whole profile (eCMWP) method. This study introduces and validates two data-driven DLPA models to extract dislocation densities from experimentally gathered whole line diffraction profiles. Using two distinct virtual diffraction models accounting for both strain and instrument induced broadening, a database of virtual diffraction whole line profiles of Ta single crystals is generated using discrete dislocation dynamics. The databases are mined to create Gaussian process regression-based surrogate models, allowing dislocation densities to be extracted from experimental profiles. The method is validated against 11 experimentally gathered whole line diffraction profiles from plastically deformed Ta polycrystals. The newly proposed model predicts dislocation densities consistent with estimates from eCMWP. Advantageously, this data driven LPA model can distinguish broadening originating from the instrument and from the dislocation content even at low dislocation densities. Finally, the data-driven model is used to explore the effect of heterogeneous dislocation densities in microstructures containing grains, which may lead to more accurate data-driven predictions of dislocation density in plastically deformed polycrystals.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effect of Hydrophilicity and Interfacial Water Structure on Particle Attachment

Oriented attachment (OA) of nanoparticles is an important and common crystallization pathway. Efforts to isolate and quantify the interparticle forces that underlie OA have only recently been initiated and the role played by the interfacial solvent structure in the confined region between nanocrystal surfaces in enabling and controlling OA remains an open question. In this work, classical molecular dynamics (MD) simulations were performed to compute the free energy landscape of nanoparticles approaching mineral substrates in both vacuum and pure water. Periclase (MgO), muscovite (KAl 3 Si 3 O 10 (OH) 2 ), and pyrophyllite (Al 2 Si 4 O 10 (OH) 2 ) nanoparticles exposing the (100), (001), and (001) surfaces, respectively, were brought to contact with substrates exposing the same surfaces. These mineral surfaces were selected to investigate a range of hydrophilicities (periclase > muscovite > pyrophyllite). The MD simulations revealed that the interfacial water structure created free energy minima for nanoparticle approach that corresponded to integer numbers of intervening water layers. The depth of the free energy minima and the free energy barriers between minima correlated positively with the hydrophilicity of the mineral surface. While the range of solvent-mediated interactions was predicted to be short (a few intervening water layers at most for MgO), the free energy barriers were calculated to be large (fraction of an eV per nm 2 ) and the effect of misalignment diminished rapidly with the number of intervening water layers. The results help explain the formation of mesocrystals and the observed ability of nanoparticles to rotate before attachment while in a long-lived solvent-separated state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

External and Internal Reconnection in Two Filament-Carrying Magnetic Cavity Solar Eruptions

We observe two near-limb solar filament eruptions. one of 2000 February 26 and the other of 2002 January 4. For both we use 195 A Fe XII images from the Extreme-Ultraviolet Imaging Telescope (EIT) and magnetograms from the Michelson Doppler Imager (MDI). both of which are on the Solar and Heliospheric Observatory. (SOHO). For the earlier event we also use soft X-ray telescope (SXT). hard X-ray telescope (HXT). and Bragg Crystal Spectrometer (BCS) data from the Yohkoh satellite. and hard X-ray data from the BATSE experiment on the Compton Gamma Ray Observatory. (CGRO). Both events occur in quadrupolar magnetic regions. and both have coronal features that we infer belong to the same magnetic cavity structures as the filaments. In both cases. the cavity and filament first rise slowly at approx. 10 km/s prior to eruption and then accelerate to approx. 100 km/s during the eruption. although the slow-rise movement for the higher altitude cavity elements is clearer in the later event. We estimate that both filaments and both cavities contain masses of approx. 10(exp14) - 1 0(exp 15) and approx. l0(exp 15) - l0(exp 16) g. respectively. We consider whether two specific magnetic reconnection-based models for eruption onset. the "tether cutting" and the "breakout" models. are consistent with our observations. In the earlier event, soft X-rays from SXT show an intensity increase during the 12 minute interval over which fast eruption begins. which is consistent with tether- cutting-model predictions. Substantial hard X-ray. however. do not occur until after fast eruption is underway. and so this is a constraint the tether-cutting model must satisfy. During the same 12 minute interval over which fast eruption begins, there are brightenings and topological changes in the corona indicative of high-altitude reconnection early in the eruption. and this is consistent with breakout predictions. In both eruptions. the state of the overlying loops at the time of onset of the fast-rise phase of the corresponding filament can be compared with expectations from the breakout model. thereby setting constraints that the breakout model must meet. Our findings are consistent with both runaway tether-cutting-type reconnection and fast breakout-type reconnection. occurring early in the fast phase of the February eruption and with both types of reconnection being important in unleashing the explosion, but we are not able to say which. if either, type of reconnection actually triggered the fast phase. In any case. we have found specific constraints that either model. or any other model. must satisfy if correct.

Sterling, Alphonse C.↗
DOE OSTI2023

Determination of the vacancy distribution over Al cation sites in γ-Al 2 O 3

Although gamma-alumina (γ-Al 2 O 3 ) is an extensively used material with wide-ranging applications due to its inherently high surface area and acidity, its atomic structure is still not fully understood. γ-Al 2 O 3 is described as having a spinel-like structure, where the O sublattice has a face-centered cubic (FCC) arrangement and Al cations are placed in the spinel tetrahedral and octahedral interstitial sites. Achieving the correct stoichiometry of Al 2 O 3 , however, requires the introduction of Al vacancies into some of the interstitial sites. Despite the importance of accurately describing the structure of γ-Al 2 O 3 , the distribution of vacancies between tetrahedral and octahedral sites remains unclear, in part because of the usually poor crystalline quality of γ-Al 2 O 3 that has often been used in previous studies. To determine the actual cation distribution in γ-Al 2 O 3 , single-crystalline γ-Al 2 O 3 was investigated using a correlative approach of experimental and simulated selected-area electron diffraction (SAED) and high-resolution electron energy-loss spectroscopy (EELS). Comparison of the reflection intensities in single-crystal SAED to simulated SAED from models with varied vacancy distributions revealed that vacancies exist primarily on tetrahedral sites, contrary to the placement of vacancies on octahedral sites proposed in several common models. Comparison of EELS spectra—acquired with the highest energy resolution reported so far for γ-Al 2 O 3 —with ab initio multiple scattering EELS simulations confirmed the distribution of vacancies on tetrahedral sites. These results enable more accurate modeling of γ-Al 2 O 3 to better predict its properties in existing and future applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Glycosidic linkage, N -acetyl side-chain, and other structural properties of methyl 2-acetamido-2-deoxy-β- D -glucopyranosyl-(1→4)-β- D -mannopyranoside monohydrate and related compounds

The crystal structure of methyl 2-acetamido-2-deoxy-β-D-glycopyranosyl-(1→4)-β-D-mannopyranoside monohydrate, C 15 H 27 NO 11 ·H 2 O, was determined and its structural properties compared to those in a set of mono- and disaccharides bearing N -acetyl side-chains in βGlcNAc aldohexopyranosyl rings. Valence bond angles and torsion angles in these side chains are relatively uniform, but C—N (amide) and C—O (carbonyl) bond lengths depend on the state of hydrogen bonding to the carbonyl O atom and N—H hydrogen. Relative to N -acetyl side chains devoid of hydrogen bonding, those in which the carbonyl O atom serves as a hydrogen-bond acceptor display elongated C—O and shortened C—N bonds. This behavior is reproduced by density functional theory (DFT) calculations, indicating that the relative contributions of amide resonance forms to experimental C—N and C—O bond lengths depend on the solvation state, leading to expectations that activation barriers to amide cis – trans isomerization will depend on the polarity of the environment. DFT calculations also revealed useful predictive information on the dependencies of inter-residue hydrogen bonding and some bond angles in or proximal to β-(1→4) O -glycosidic linkages on linkage torsion angles φ and ψ. Hypersurfaces correlating φ and ψ with the linkage C—O—C bond angle and total energy are sufficiently similar to render the former a proxy of the latter.

Chemistry↗
NASA NTRS2004

External and Internal Reconnection in Two Filament-Carrying Magnetic-Cavity Solar Eruptions

We observe two near-limb solar filament eruptions, one of 2000 February 26 and the other of 2002 January 4. For both we use 195 Angstroms Fe XII images from the Extreme-Ultraviolet (EUV) Imaging Telescope (EIT) and magnetograms from the Michelson Doppler Imager (MDI), both on the Solar and Heliospheric Observatory (SOHO) satellite. For the earlier event we also use soft X-ray telescope (SXT), hard X-ray telescope (HXT), and Bragg Crystal Spectrometer (BCS) data from the Yohkoh satellite, and hard X-ray data from the BATSE experiment on the Compton Gamma Ray Observatory (CGRO). Both events occur in quadrupolar magnetic regions, and both have coronal features that we infer belong to the same magnetic-cavity structures as the filaments. In both cases the cavity and filament first rise slowly at approximately 10 kilometers per second prior to eruption, and then accelerate to approximately 100 kilometers per second during the eruption, although the slow-rise movement for the higher-altitude cavity elements is clearer in the later event. We estimate both filaments and both cavities to contain masses of approximately 10(exp 14-15) g and approximately 10(exp 15-16) g respectively. We consider whether two specific magnetic-reconnection-based models for eruption onset, the tether cutting and the breakout models, are consistent with our observations. In the earlier event soft X-rays from SXT show an intensity increase during the 12-minute interval over whch fast eruption begins, which is consistent with tether-cutting-model predictions. Substantial hard X-rays, however, do not occur until after fast eruption is underway, and so this is a constraint the tether-cutting model must satisfy. During the same 12-minute interval over which fast eruption begins, there are brightenings and topological changes in the corona indicative of high-altitude reconnection early in the eruption, and this is consistent with breakout predictions. In both eruptions, however, the onset of the filament fast-rise phase occurs while overlying cavity-related coronal loops are still evolving from a "closed" state to an "open" state, and our observations of the time evolution of these loops compared to the eruption state in both events are constraints the breakout model must meet. Therefore our findings are consistent with runaway-tether-cutting-type reconnection and fast breakout-type reconnection both occurring early in the fast phase of the February eruption and with both types of reconnection being important in unleashing the explosion, but we are not able to say which, if either, type of reconnection actually triggered the fast phase. We have also found specific constraints that either model, or any other model, must satisfy if correct.

Sterling, Alphonse C.↗
NASA NTRS2004

External and Internal Reconnection in Two Filament-Carrying Magnetic-Cavity Solar Eruptions

We observe two near-limb solar filament eruptions, one of 2000 February 26 and the other of 2002 January 4. For both we use 195 Angstroms, Fe XII images from the Extreme-Ultraviolet Imaging Telescope (EIT) and magnetograms from the Michelson Doppler Imager (MDI), both of which are on the Solar arid Heliospheric Observatory (SOHO). For the earlier event we also use soft X-ray telescope (SXT), hard X-ray telescope (HXT), and Bragg Crystal Spectrometer (BCS) data from the Yohkoh satellite, and hard X-ray data from the BATSE experiment on the Compton Gamma Ray Observation, (CGRO). Both events occur in quadrupolar magnetic regions, and both have coronal features that we infer belong to the same magnetic cavity structures as the filaments. In both cases, the cavity and filament first rise slowly at approximately 10 kilometers per second prior to eruption and then accelerate to approximately 100 kilometers per second during the eruption, although the slow-rise movement for the higher altitude cavity elements is clearer in the later event. We estimate that both filaments and both cavities contain masses of approximately 10(exp 14)-10(exp 15) and approximately 10(exp 15)-10(exp 16)g, respectively. We consider whether two specific magnetic reconnection-based models for eruption onset, the tether cutting and the breakout models, are consistent with our observations. In the earlier event, soft X-rays from SXT show an intensity increase during the 12 minute interval over which fast eruption begins, which is consistent with tether-cutting-model predictions. Substantial hard X-rays, however, do not occur until after fast eruption is underway, and so this is a constraint the tether-cutting model must satisfy. During the same 12 minute interval over which fast eruption begins, there are brightenings and topological changes in the corona indicative of high-altitude reconnection early in the eruption, and this is consistent with breakout predictions. In both eruptions, the state of the overlying loops at the time of onset of the fast-rise phase of the corresponding filament can be compared with expectations from the breakout model, thereby setting constraints that the breakout model must meet. Our findings are consistent with both runaway tether-cutting-type reconnection and fast breakout-type reconnection, occurring early in the fast phase of the February eruption and with both types of reconnection being important in unleashing the explosion, but we are not able to say which, if either, type of reconnection actually triggered the fast phase. In any case, we have found specific constraints that either model, or any other model, must satisfy if correct.

Sterling, Alphonse C.↗