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At least 19 records

Comparative Study of Solvatomorphs of Stryker's Reagent Using MicroED and Quantum Mechanics

Abstract The atomic position of hydrogen atoms in metal hydrides has been a long‐standing structural question in inorganic chemistry given that hydride delivery is integral to diverse chemical reactions. Microcrystal electron diffraction (microED), with it's increased sensitivity toward hydrogen atoms relative to X‐ray diffraction, offers a potential path to addressing this challenge. Herein, the first microED study of Stryker's reagent is reported, resulting in the structure of a new benzene solvate. Improved accuracy for hydrogen atom positions was obtained via a quantum crystallography (QCr) approach, Hirshfeld atom refinement (HAR). Structural and topological analysis supports edge bridging hydrides in the microED structure of a THF solvate form, consistent with previous diffraction studies. Interestingly, analysis of a new benzene solvate, discovered in this study, is consistent with mixed edge‐ and face‐bridging hydrides.

Jha, Kunal K. [Division of Chemistry &amp, Chemica

Electronic structure of the honeycomb iridate Cu 2 ⁢IrO 3 at high pressure

Cu 2 IrO 3 has attracted recent interest due to its proximity to the Kitaev quantum spin liquid state and the complex structural response observed at high pressures. We use x-ray spectroscopy and scattering as well as electrical transport techniques to unveil the electronic structure of Cu 2 IrO 3 at ambient and high pressures. Despite featuring a Ir 4+ J eff = 1/2 state at ambient pressure, Ir L 3 -edge resonant inelastic x-ray scattering reveals broadened electronic excitations that point to the importance of Ir 5d-Cu 3d interaction. High pressure first drives an Ir-Ir dimer state with collapsed < L · S > and < L z >/< S z >, signaling the formation of 5d molecular orbitals. A novel Cu → Ir charge transfer is observed above 30 GPa at low temperatures, leading to an approximate Ir 3+ and Cu 1.5+ valence, with persistent insulating electrical transport seemingly driven by charge segregation of Cu 1+ /Cu 2+ ions into distinct sites. Concomitant x-ray spectroscopy and diffraction measurements through different thermodynamic paths demonstrate a strong electron-lattice coupling, with J eff = 1/2 and Ir 3+ /Cu 1.5+ electronic states occurring only in phases 1 and 5, respectively. Remarkably, the charge-transfer state can only be reached if Cu 2 IrO 3 is pressurized at low temperature, suggesting that phonons play an important role in the inhibiting this phase. Furthermore, these results point to the choice of thermodynamic path across interplanar collapse transition as a key parameter to access novel states in intercalated iridates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Achieving a near-ideal silicon crystal neutron interferometer using submicrometer fabrication techniques

Perfect-crystal neutron interferometry, which is analogous to Mach-Zehnder interferometry, uses Bragg diffraction to form interfering neutron paths. The measured phase shifts can be used to probe many types of interactions whether it be nuclear, electromagnetic, gravitational, or topological in nature. For a perfect-crystal interferometer to preserve coherence, the crystal must possess a high degree of dimensional tolerance as well as being relatively defect-free with minimal internal stresses. In the past, perfect-crystal neutron interferometers have been produced by a two-step process. First, a resin diamond wheel would be used to remove excess material and shape the interferometer. Afterword, the crystal would be etched to remove surface defects and elevate strains. This process has had limitations in terms of repeatability and in maximizing the final contrast, or fringe visibility, of the interferometer. We have tested various fabrication and post-fabrication techniques on a single perfect-crystal neutron interferometer and measured the interferometer's performance at each step. Here we report a robust, nonetching fabrication process with high final contrast. For the interferometer used in this work, we achieved contrasts of greater than 90% several times and ultimately finished with an interferometer that has 92% contrast and a uniform phase distribution. Published by the American Physical Society 2024

Huber, M. G. (ORCID:0000000237958445)

Effective field theory factorization for diffraction

We derive a factorization formula for coherent and incoherent ep diffraction using the soft collinear effective theory, utilizing multiple power expansion parameters to handle different kinematic regions. This goes beyond the known hard-collinear diffractive factorization to address the small-x Regge dynamics and Pomeron exchange from first principles. The effective field theory analysis also uncovers and factorizes an important irreducible incoherent background generated by color-nonsinglet exchange, dubbed “quasi-diffraction”, for which we calculate the associated Sudakov suppression. For unpolarized scattering we show that there are four diffractive structure functions at leading power, and point out the importance of studying ${F}_{3,4}^D$ through asymmetries, in addition to ${F}_{2,L}^D$. For the quasi-diffractive background, we make model independent predictions for ratios of the corresponding structure functions in a perturbative kinematic region. Our analysis also makes predictions for six leading-power spin-dependent structure functions. Finally, we provide connections to diffractive parton distributions, and assess the Ingelman-Schlein model. Our work lays a path for further QCD-based studies of diffraction.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS

FUSE/Lyman grant

A variety of options for a short wavelength spectrometer for the Lyman telescope has been studied, and the optimum configuration for this instrument identified. In this spectrometer option study it is assumed (consistent with performance goals outlined by the project) that the instrument, whose prime spectral domain is 900-12000A, will incorporate a grazing incidence telescope which will maintain good collecting efficiency down to 100A. In particular it is assumed that the telescope will have an effective focal length of 10 meters, an image quality of 1.5", and will provide a diverging f/10 beam. Designs compatible with this telescope are analyzed, and it is determined that a two-element grazing incidence spectrometer using as its first optic an ellipsoid to re-focus the beam and a varied line-space plane diffraction grating to disperse the light is the best overall design. This spectrometer could be fed by a small pick-off mirror located just behind the prime focus of the telescope and would clear the light path when not in use. A test of the diffraction efficiency of a low blaze angle grating is undertaken, which is the only technical uncertainty in the spectrometer design.

Hurwitz, M.

Higher-order parabolic approximations for sound propagation in stratified moving media

Asymptotic solutions of order k-n are developed for the equations governing the propagation of sound through a stratified moving medium. Here k is a dimensionless wave number and n is the arbitrary order of the approximation. These approximations are an extension of geometric acoustics theory and provide corrections to that theory in the form of multiplicative functions which satisfy parabolic partial differential equations. These corrections account for the diffraction effects caused by variation of the field normal to the ray path and the interaction of these transverse variations with the variation of the field along the ray. The theory is illustrated by application to simple examples.

Mcaninch, G. L.

Higher order parabolic approximations of the reduced wave equation

Asymptotic solutions of order k to the nth are developed for the reduced wave equation. Here k is a dimensionless wave number and n is the arbitrary order of the approximation. These approximations are an extension of geometric acoustics theory, and provide corrections to that theory in the form of multiplicative functions which satisfy parabolic partial differential equations. These corrections account for the diffraction effects caused by variation of the field normal to the ray path and the interaction of these transverse variations with the variation of the field along the ray. The theory is applied to the example of radiation from a piston, and it is demonstrated that the higher order approximations are more accurate for decreasing values of k.

Mcaninch, G. L.

Chemical Vapor Deposition-Grown Hexagonal Boron Nitride and Graphene for Tandem Dielectric Capacitive Polymer Devices

To address the low energy density of polymeric capacitors, this work explores how tandem combinations of antagonistic properties can enhance energy storage. We introduce multilayer architecture integrating chemical vapor deposition (CVD)-grown ≈2 nm hexagonal boron nitride (hBN) and graphene with ferroelectric polyvinylidene fluoride (PVDF) and linear polyetherimide (PEI) layers to suppress leakage paths, reduce loss, and promote Maxwell–Wagner–Sillars polarization. Raman spectroscopy, X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and plasma focused ion beam (PFIB) analyses confirm robust material integration. In conclusion, for the tandem device, E BD ≈600 V/μm, while individual layers show lower values (PVDF|Graphene (Gr)|PVDF ≈ 50 V/μm and PEI|hBN|PEI ≈ 275 V/μm), yielding an overall ≈6000% enhancement and demonstrating the effectiveness of the 2D multilayer design.

Chemical vapor deposition (CVD)

The effect of yttrium and thorium on the oxidation behavior of Ni-Cr-Al alloys

The effect of quaternary additions of 0.5% Y, 0.5 and 1.0% Th to a base alloy of Ni-10CR-5Al on the oxidation behavior and mechanism was studied during oxidation in air over the range of 1000 to 1200 C. The presence of yttrium decreased the oxidation kinetics slightly, whereas, the addition of thorium caused a slight increase. Oxide scale adherence was markedly improved by the addition of the quaternary elements. Although a number of oxides formed on yttrium containing alloys, quantitative X-ray diffraction clearly showed that the rate-controlling step was the diffusion of aluminum through short circuit paths in a thin layer of alumina that formed parabolically with time. Although the scale adherence of the yttrium containing alloy was considerably better than the base alloys, spalling did occur that was attributed to the formation of the voluminous YAG particles which grew in a mushroom-like manner, lifting the protective scale off the subrate locally. The YAG particles formed primarily at grain boundaries in the substrate in which the yttrium originally existed as YNi9.

Kumar, A.

Optical efficiency of far-infrared photoconductors

The present optimization of the geometry of far-IR photoconductive detectors with diffraction-limited throughput, on the basis of experimental and theoretical results, gives attention to the internal optical path relative to measured absorption length, photoconductive gain, uniformity of illumination, cosmic ray cross section, and design compatibility with the requirements of one- and two-dimensional arrays. It is demonstrated that a rod-shaped, square cross section detector geometry, having lateral face electrodes and a beveled backface with which to trap the radiation by total internal reflection, exhibits responsivity commensurate with that of the best available detectors in integrating cavities.

Wang, J.-Q.

Dispersion Leverage Coronagraph: a nulling coronagraph for use on primary objective grating telescopes

Here, we present the Dispersion Leverage Coronagraph (DLC), a variation of the Achromatic Interfero Coronagraph (AIC) that is designed for optical systems featuring large, dispersive primary objective gratings. DLC was originally designed for the Diffractive Interfero Coronagraph Exoplanet Resolver (DICER), a notional 20 m class infrared space telescope utilizing the enhanced one-dimensional angular resolution of large diffraction gratings to discover and characterize near-Earth exoplanets. Here we develop the theoretical foundation for DLC, and apply it to DICER as an example use case. We derive important properties of the DLC system, including focal plane transmission maps, stellar leakage, residual optical path difference tolerance, and pointing error/jitter considerations. Ultimately, we found that DLC effectively nulls an on-axis target across the entire spectrum in the focal plane, allowing for 2D/λ diffraction-limited imaging. It requires asymmetrical fine-guidance tolerances on pointing error/jitter. We work through a benchmark DICER design, explaining the need for a second disperser to reduce background from Zodiacal light, and showing that it could plausibly find and characterize ∼4 nearby, habitable exoplanets around Sun-like stars in a 7-year mission; about 30% of the habitable exoplanets within 8 pc were found in our simulation. The DLC may be useful for any application requiring extremely high-resolution, close companion spectroscopy.

AIC

Path integral molecular dynamics: A high-fidelity approach to quantum dynamics of electrons

We investigate electron transport in the uniform electron gas using ring-polymer molecular dynamics (RPMD). Working in the weakly coupled, non-degenerate regime, we use RPMD to probe how the onset of quantum diffraction effects at high temperature reshapes electron–electron collisions and leads to a classical-to-quantum crossover in macroscopic transport properties. Static thermodynamics obtained with RPMD are consistent with the weak-coupling equation of state, confirming correct quantum Boltzmann sampling. Real-time transport extracted from mean square displacements exhibits the expected ballistic-to-diffusive transition and a systematic reduction of the electronic self-diffusivity as quantum effects strengthen, due to quantum diffraction modifying electron–electron collisions. Direct ring-polymer scattering simulations reveal diffractive “softening” of binary deflections, providing a micro-to-macro link between collision physics and diffusion. The present study establishes RPMD as a quantitative, trajectory-based tool for electron transport across the classical–quantum crossover and furnishes benchmarks for improving Coulomb-log interpolation models. We outline extensions to multi-component plasmas and a path to incorporate Fermi–Dirac statistics within path-integral dynamics.

Electronic transport

Formation of distinctive nanostructured metastable polymorphs mediated by kinetic transition pathways in germanium

High-pressure β -Sn germanium may transform into diverse metastable allotropes with distinctive nanostructures and unique physical properties via multiple pathways under decompression. However, the mechanism and transition kinetics remain poorly understood. Here, we investigate the formation of metastable phases and nanostructures in germanium via controllable transition pathways of β -Sn Ge under rapid decompression at different rates. High-resolution transmission electron microscopy reveals three distinct metastable phases with the distinctive nanostructures: an almost perfect st12 Ge crystal, nanosized bc8/r8 structures with amorphous boundaries, and amorphous Ge with nanosized clusters (0.8–2.5 nm). Fast in situ x-ray diffraction and x-ray absorption measurements indicate that these nanostructured products form in certain pressure regions via distinct kinetic pathways and are strongly correlated with nucleation rates and electronic transitions mediated by compression rate, temperature, and stress. This work provides deep insight into the controllable synthesis of metastable materials with unique crystal symmetries and nanostructures for potential applications.

36 MATERIALS SCIENCE

Concave holographic grating for spectrographic applications: Study of the aberrations

An analysis of reflecting diffraction gratings by the application of holographic techniques is presented. The subjects discussed are: (1) holographic grating properties, (2) calculation of aberrant optical path, (3) analytical expression of stigmatic points, (4) spherical aberration and limitation of grating width, and (5) determination of construction parameters.

Pieuchard, G.

Propeller modulation effects on a scanning beam microwave landing system

An investigation to assess the modulation effects on microwave signals transmitted through rotating propeller blades. Interruption of the antenna line-of-sight signal by the rotating propeller causes a variation of path loss, which produces essentially an amplitude modulation of the received signal. This interruption or blockage effect is generally only partial because of edge diffraction around the particular interfering propeller blade. Signals reflected from the rotating propeller will also cause Doppler frequency shifts to be present in the received signals. A scanning beam microwave landing system (MLS) known as MODILS (modular instrument landing system) was used to process the received signals for display. The effects of propeller modulation were studied by varying the following parameters: (1) spacing between propeller and receiving antenna, (2) propeller dimensions, (3) propeller speed (rpm), (4) number of propeller blades, (5) system data rate, (6) receiver response time, and (7) receiver antenna aperture.

Pope, J. M.

Ray-tracing the convex curved crystal X-ray spectrograph

The convex curved crystal X-ray spectrograph has recently seen increasing use for the spectral analysis of transient plasmas. The present paper describes the calculation of ray paths through the spectrograph for both localized and extended sources. The method traces a ray from any given source point to its point of diffraction by the curved crystal and then to the imaging circle, where the image point is obtained. Application of the ray tracing method is made to some actual experimental configurations to obtain resolution values and source sizes. Wavelength calibrations are obtainable with the ray tracing method in advance of instrument construction.

Kastner, S. O.