Optimized Microwave-Based Synthesis of Thermally Stable Inverse Catalytic Core-shell Motifs for CO2 Hydrogenation
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99 GENERAL AND MISCELLANEOUS↗
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Muon Tomography of Deep Reservoirs
Imaging subsurface geological formations, oil and gas reservoirs, mineral deposits, cavities or magma chambers under active volcanoes has been for many years a major quest of geophysicists and geologists. Since these objects cannot be observed directly, different indirect geophysical methods have been developed. They are all based on variations of certain physical properties of the subsurface that can be detected from the ground surface or from boreholes. Electrical resistivity, seismic wave’s velocities and density are certainly the most used properties. If we look at density, indirect estimates of density distributions are performed currently by seismic reflection methods - since the velocity of seismic waves depend also on density - but they are expensive and discontinuous in time. Direct estimates of density are performed using gravimetric data looking at variations of the gravity field induced by the density variations at depth but this is not sufficiently accurate. A new imaging technique using cosmic-ray muon detectors has emerged during the last decade and muon tomography - or muography - promises to provide, for the first time, a complete and precise image of the density distribution in the subsurface. Further, this novel approach has the potential to become a direct, real-time, and low-cost method for monitoring fluid displacement in subsurface reservoirs.
borehole detector↗
Refined Mass and Geometric Measurements of the High-mass PSR J0740+6620
We report results from continued timing observations of PSR J0740+6620, a high-mass, 2.8 ms radio pulsar in orbit with a likely ultracool white dwarf companion. Our data set consists of combined pulse arrival-time measurements made with the 100 m Green Bank Telescope and the Canadian Hydrogen Intensity Mapping Experiment telescope. We explore the significance of timing-based phenomena arising from general relativistic dynamics and variations in pulse dispersion. When using various statistical methods, we find that combining∼1.5 yr of additional, high-cadence timing data with previous measurements confirms and improves on previous estimates of relativistic effects within the PSR J0740+6620 system, with the pulsar mass=-+mM2.08p0.070.07 M (68.3% credibility) determined by the relativistic Shapiro time delay. For the first time, we measure secular variation in the orbital period and argue that this effect arises from apparent acceleration due to significant transverse motion. After incorporating contributions from Galactic differential rotation and off-plane acceleration in the Galactic potential, we obtain a model-dependent distance of=-+d1.140.150.17kpc (68.3% credibility). This improved distance confirms the ultracool nature of the white dwarf companion determined from recent optical observations. We discuss the prospects for future observations with next-generation facilities, which will likely improve the precision on mp for J0740+6620 by an order of magnitude within the next few years
Neutron stars↗
Iterative Joint Ptychography-Tomography with Total Variation Regularization
In order to determine the 3D structure of a thick sample, researchers have recently combined ptychography (for high resolution) and tomography (for 3D imaging) in a single experiment. 2-step methods are usually adopted for reconstruction, where the ptychography and tomography problems are often solved independently. In this paper, we provide a novel model and ADMM-based algorithm to jointly solve the ptychography-tomography problem iteratively, also employing total variation regularization. The proposed method permits large scan stepsizes for the ptychography experiment, requiring less measurements and being more robust to noise with respect to other strategies, while achieving higher reconstruction quality results.
2-step methods↗
High and Ultra-High Temperature Reaction Kinetics by Single Nanoparticle Mass Spectrometry
Methodology is presented for non-destructive, optically-detected single nanoparticle (NP) mass spectrometry, with the goal of extracting surface reaction kinetics for single NPs at high temperatures. Methods for determining the NP charge, mass, and temperature as a function of time are discussed, and the data are used to extract both the absolute kinetics for mass change, as well as the efficiencies of the surface processes that cause them. Factors that contribute to the uncertainties in absolute and relative mass determination, and in the resulting kinetic parameters, are discussed. The method allows the NP-to-NP variations in initial reactivity to be measured directly, along with the time evolution of reactivity resulting from NP structural/compositional changes that occur under reaction conditions. The strengths and limitations of single nanoparticle mass spectrometry as a high temperature surface kinetics tool are discussed in the context of sublimation and O2 oxidation kinetics experiments for single hafnium (Hf) NPs at temperatures ranging above 2400 K. The Hf oxidation kinetics are compared to analogous oxidation experiments for silicon, graphite, and carbon black NPs. In all four cases, the oxidation chemistry was dominated by processes that result in net mass loss, and the distinct mechanisms responsible are discussed. All four NPs also eventually passivated, i.e., the efficiencies for oxidative etching decreased by at least two orders of magnitude, relative to the initial efficiencies. Furthermore, the passivation mechanisms, which are quite different for carbon, compared to silicon or hafnium, are discussed. Carbon NP passivation is attributed to structural isomerization leading to fully coordinated, fullerene-like NP surfaces, while for silicon and hafnium, passivation results from delayed formation of an oxide layer, triggered by accumulation of oxygen in the NP sub-surface region.
36 MATERIALS SCIENCE↗
Robust Approaches to Handling Complex Geometries with Galerkin Difference Methods
The Galerkin difference (GD) basis is a set of continuous, piecewise polynomials defined using a finite-difference-like grid of degrees of freedom. The one dimensional GD basis functions are naturally extended to multiple dimensions using a tensor product construction on quadrilateral elements. The GD basis can be used to define the solution space for a discontinuous Galerkin finite element discretization of partial differential equations. In this work we propose two approaches to handling complex geometries within this setting: (1) using nonconforming, curvilinear GD elements and (2) coupling affine GD elements with curvilinear simplicial elements. In both cases the (semidiscrete) discontinuous Galerkin method is provably energy stable even when variational crimes are committed. Additionally, for both element types a weight-adjusted mass matrix is used, which ensures that only the reference mass matrix must be inverted. We also present sufficient conditions on the treatment of metric terms for the curvilinear, nonconforming GD elements to ensure that the scheme is both constant preserving and conservative. Numerical experiments confirm the stability results and demonstrate the accuracy of the coupled schemes.
97 MATHEMATICS AND COMPUTING↗
Excited State Specific Multi-Slater Jastrow Wave Functions
We combine recent advances in excited state variational principles, fast multi-Slater Jastrow methods and selective configuration interaction, to create multi-Slater Jastrow wave function approximations that are optimized for individual excited states. In addition to the Jastrow variables and linear expansion coefficients, this optimization includes state-specific orbital relaxations in order to avoid the compromises necessary in state-averaged approaches. Here, we demonstrate that, when combined with variance matching to help balance the quality of the approximation across different states, this approach delivers accurate excitation energies even when very modest multi-Slater expansions are used. Intriguingly, this accuracy is maintained even when we study a difficult chlorine-anion-to-π* charge transfer in which traditional state-averaged multireference methods must contend with different states that require drastically different orbital relaxations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Entangled Electrons Drive a Non-superexchange Mechanism in a Cobalt Quinoid Dimer Complex
A central theme in chemistry is the understanding of the mechanisms that drive chemical transformations. A well-known, highly cited mechanism in organometallic chemistry is the superexchange mechanism in which unpaired electrons on two or more metal centers interact through an electron pair of the bridging ligand. We use a combination of novel synthesis and computation to show that such interactions may in fact occur by a more direct mechanism than superexchange that is based on direct quantum entanglement of the two metal centers. Specifically, we synthesize and experimentally characterize a novel cobalt dimer complex with benzoquinoid bridging ligands and investigate its electronic structure with the variational two-electron reduced density matrix method using large active spaces. The result draws novel connections between inorganic mechanisms and quantum entanglement, thereby opening new possibilities for the design of strongly correlated organometallic compounds whose magnetic and spin properties have applications in superconductors, energy storage, thermoelectrics, and spintronics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Seismic Velocity Change Patterns Along the San Jacinto Fault Zone Following the 2010 M 7.2 El Mayor–Cucapah and M 5.4 Collins Valley Earthquakes
We study temporal changes of seismic velocity (d v /v ) in the crust around the central section of the San Jacinto fault zone (SJFZ), Southern California. Focusing on a 200-day-long period around April 2010, our analysis resolves two tens-of-days-long successive episodes of reduced velocities that are compatible with signals from the long base strainmeter at the Piñon Flat Observatory. The imaged d v /v sequences are proxies for evolving material properties in the crust surrounding the SJFZ. The temporal and the spatial coincidence of the observed d v /v patterns with the occurrence of two proposed creep episodes suggest that the relative velocity changes reflect the response to deep creep events that follow the M 7.2 El Mayor-Cucapah earthquake and the M 5.4 Collins Valley earthquake that occurred 94 days later on the San Jacinto fault. The main slip during the creep events was proposed to occur below 10-km depth. Wavefield properties suggest sensitivity to medium changes above this source zone, in the top 10 km. The distribution of the obtained d v /v reductions shows a strong difference between large values to the west of the SJFZ and significantly smaller amplitudes to the east. The similarity to the seasonal velocity change pattern implies that the results are likely controlled by the contrast of mechanical properties across the fault, such as fault-perpendicular shear modulus variations. Our analysis extends the spectrum of methods that can be used to study earthquake interaction, fault zone rheology and dynamics, triggering, and the interplay between creep episodes and earthquakes.
58 GEOSCIENCES↗
Durability Research Is Pivotal for Perovskite Photovoltaics
Metal halide perovskite solar cells have shown promising power conversion efficiencies, but commercialization requires that decent durability is also demonstrated. Under normal operation, solar cells are subject to a complex combination of stressors, such as visible light, ultraviolet light, heat, humidity, mechanical stress and electric potential, which complicates the understanding of failure mechanisms. Existing stress tests do not act as a time machine. In new materials systems such as perovskite photovoltaics, the tests have no known relationship to field service. In this Perspective we recommend following a durability learning cycle that interleaves photovoltaic module engineering with field testing; accelerated testing; and preconditioning and performance engineering. We advocate for field testing to demonstrate real-world performance and identify field-relevant failure modes, and urge the community to develop accelerated and qualification tests that account for device metastability, variations in material composition and different/various processing methods. In conclusion, these practices are more difficult, but more important, than the simple pursuit of higher initial efficiencies.
14 SOLAR ENERGY↗
The role of rotation-vibration coupling in symmetric and asymmetric isotopomers of ozone
A theoretical framework and a computer code (SpectrumSDT) are developed for accurate calculations of coupled rotational–vibrational states in triatomic molecules using hyper-spherical coordinates and taking into account the Coriolis coupling effect. Concise final formulas are derived for the construction of the Hamiltonian matrix using an efficient combination of the variational basis representation and discrete variable representation methods with locally optimized basis sets and grids. First, the new code is tested by comparing its results with those of the APH3D program of Kendrick et al. [Kendrick, Pack, Walker, and Hayes, J. Chem. Phys. 110, 6673 (1999)]. Then, accurate calculations of the rovibrational spectra are carried out for doubly substituted symmetric ( 18 O 16 O 18 O) and asymmetric ( 18 O 18 O 16 O) ozone isotopomers for the total angular momentum up to J = 5. Together with similar data recently reported for the singly substituted symmetric ( 16 O 18 O 16 O) and asymmetric ( 16 O 16 O 18 O) ozone isotopomers, these calculations quantify the role of the Coriolis coupling effect in the large mass-independent isotopic enrichment of ozone, observed in both laboratory experiments and the atmosphere of the Earth. It is found that the Coriolis effect in ozone is relatively small, as evidenced by deviations of its rotational constants from the symmetric-top-rotor behavior, magnitudes of parity splittings (Λ-doubling), and ratios of rovibrational partition functions for asymmetric vs symmetric ozone molecules. It is concluded that all of these characteristics are influenced by the isotopic masses as much as they are influenced by the overall symmetry of the molecule. It is therefore unlikely that the Coriolis coupling effect could be responsible for symmetry-driven mass-independent fractionation of oxygen isotopes in ozone.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Stochastic evaluation of fourth-order many-body perturbation energies
A scalable, stochastic algorithm evaluating the fourth-order many-body perturbation (MP4) correction to energy is proposed. Three hundred Goldstone diagrams representing the MP4 correction are computer generated and then converted into algebraic formulas expressed in terms of Green’s functions in real space and imaginary time. They are evaluated by the direct (i.e., non-Markov, non-Metropolis) Monte Carlo (MC) integration accelerated by the redundant-walker and control-variate algorithms. The resulting MC-MP4 method is efficiently parallelized and is shown to display O(n 5.3 ) size-dependence of cost, which is nearly two ranks lower than the O(n 7 ) dependence of the deterministic MP4 algorithm. Furthermore, it evaluates the MP4/aug-cc-pVDZ energy for benzene, naphthalene, phenanthrene, and corannulene with the statistical uncertainty of 10 mE h (1.1% of the total basis-set correlation energy), 38 mE h (2.6%), 110 mE h (5.5%), and 280 mE h (9.0%), respectively, after about 10 9 MC steps.
74 ATOMIC AND MOLECULAR PHYSICS↗
A comparative study of structural similarity and regularization for joint inverse problems governed by PDEs
Joint inversion refers to the simultaneous inference of multiple parameter fields from observations of systems governed by single or multiple forward models. In many cases these parameter fields reflect different attributes of a single medium and are thus spatially correlated or structurally similar. By imposing prior information on their spatial correlations via a joint regularization term, we seek to improve the reconstruction of the parameter fields relative to inversion for each field independently. One of the main challenges is to devise a joint regularization functional that conveys the spatial correlations or structural similarity between the fields while at the same time permitting scalable and efficient solvers for the joint inverse problem. We describe several joint regularizations that are motivated by these goals: a cross-gradient and a normalized cross-gradient structural similarity term, the vectorial total variation, and a joint regularization based on the nuclear norm of the gradients. Based on numerical results from three classes of inverse problems with piecewise-homogeneous parameter fields, we conclude that the vectorial total variation functional is preferable to the other methods considered. Besides resulting in good reconstructions in all experiments, it allows for scalable, efficient solvers for joint inverse problems governed by PDE forward models.
97 MATHEMATICS AND COMPUTING↗
Optimization of sporulation and purification methods for sporicidal efficacy assessment on Bacillus spores
Abstract Validating the efficacy of sporicidal agents is a critical step in current good manufacturing practices for disinfection requirements. A limitation is that the poor quality of spores can lead to false positive sporicidal results. The aim of this study was to explore optimal sporulation and purification methods in Bacillus spores. Spores of 7 Bacillus strains were produced in 5 different sporulation media. After density centrifugation, spore yields were measured by phase-contrast microscopy and enumeration assays. Effects of purification methods including heat, sonication and lysozyme, and maturation on spore qualities were determined by sodium hypochlorite sporicidal assay. Difco sporulation media was identified as the preferred sporulation medium for 4 out of 7 tested Bacillus strains. Sporulation rates in B. cereus, B. sphaericus, and B. thuringiensis were higher at 30°C than the rates at 37°C at a difference of 5%, 65%, and 20%, respectively. Bacillus licheniformis favored Mn2+-amended 10% Columbia Broth at 37°C for sporulation with 40–72% higher sporulation rates than other media. The maximum sporulation rates of B. cereus and B. thuringiensis were observed on double-strength Schaeffer's-glucose broth. All studied purification methods improved the spore purity with strain variations. However, intense heat (80°C for 20 min) and lysozyme (100 μg/mL) treatment impaired the spore quality of specific Bacillus strains by sensitizing them against sodium hypochlorite. The length of the maturation period had an impact on the spore resistance, and the most optimal maturation periods ranged from 7 to 21 days in Bacillus strains. The results of this study will pave the way for further evaluation of the sporicidal activity of disinfectants.
Biotechnology & Applied Microbiology↗
Tetraquarks made of sufficiently unequal-mass heavy quarks are bound in QCD
Tetraquarks, bound states composed of two quarks and two antiquarks, have been the subject of intense study but are challenging to understand from first principles. We apply variational and Green’s function Monte Carlo methods to compute tetraquark ground-state energies in potential nonrelativistic QCD using a wide range of color and spatial wave functions. We find no evidence for bound tetraquarks composed of equal-mass quarks and antiquarks. Conversely, we find clear evidence for the existence of bound tetraquarks for sufficiently unequal quark/antiquark mass ratios at all overall mass scales where our effective theory results are applicable. We predict the critical mass ratios for bound state formation and study tetraquark bound states’ spatial and color structure at leading order and next-to-leading order in potential nonrelativistic QCD. Published by the American Physical Society 2024
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
PyMDA : microcrystal data assembly using Python
The recent developments at microdiffraction X-ray beamlines are making microcrystals of macromolecules appealing subjects for routine structural analysis. Microcrystal diffraction data collected at synchrotron microdiffraction beamlines may be radiation damaged with incomplete data per microcrystal and with unit-cell variations. A multi-stage data assembly method has previously been designed for microcrystal synchrotron crystallography. Here the strategy has been implemented as a Python program for microcrystal data assembly ( PyMDA ). PyMDA optimizes microcrystal data quality including weak anomalous signals through iterative crystal and frame rejections. Beyond microcrystals, PyMDA may be applicable for assembling data sets from larger crystals for improved data quality.
36 MATERIALS SCIENCE↗
In situ Raman spectroscopy of pressure-induced phase transformations in polycrystalline TbPO 4 , DyPO 4 , and Gd x Dy (1– x ) PO 4 [ In situ Raman spectroscopy of pressure-induced phase transformations in DyPO 4 and Gd x Dy (1– x ) PO 4 ]
Xenotime DyPO 4 and Gd x Dy (1–x) PO 4 (x = 0.4, 0.5, 0.6) (tetragonal I41amd zircon structure) have been studied at ambient temperature under high pressures inside a diamond anvil cell with in situ Raman spectroscopy. The typical Raman–active modes of the xenotime structure were observed at low pressures and the appearance of new Raman peaks at higher pressures indicated a phase transformation to a lower symmetry structure—likely monoclinic. Raman mode softening was observed, resulting in a line crossing at approximately 7–8 GPa for each material and preceding the phase transformation. The onset of phase transformation for DyPO 4 occurred at a pressure of 15.3 GPa. DyPO 4 underwent a reversible phase transformation and returned to the xenotime phase after decompression. The transformation pressures of the solid solutions (Gd x Dy (1–x) PO 4 ) were in the range 10–12 GPa. The GdxDy(1–x)PO 4 solid solutions yielded partially reversible phase transformations, retaining some of the high–pressure phase spectrum while reforming xenotime peaks during decompression. The substitution of Gd into DyPO 4 decreased the transformation pressure relative to pure DyPO 4 . In conclusion, the ability to modify the phase transformation pressures of xenotime rare–earth orthophosphates by chemical variations of solid solutions may provide additional methods to improve the performance of ceramic matrix composites.
36 MATERIALS SCIENCE↗
Focused‐beam X‐ray fluorescence and diffraction microtomographies for mineralogical and chemical characterization of unsectioned extraterrestrial samples
Abstract This study describes the application of new synchrotron X‐ray fluorescence (XRF) and diffraction (XRD) microtomographies for the 3‐D visualization of chemical and mineralogical variations in unsectioned extraterrestrial samples. These improved methods have been applied to three compositionally diverse chondritic meteorite samples that were between 300 and 400 μm in diameter, including samples prepared from fragments of the CR2 chondrite LaPaz Icefield (LAP) 02342, H5 chondrite MacAlpine Hills (MAC) 88203, and the CM2 chondrite Murchison. The synchrotron‐based XRF and XRD tomographies used are focused‐beam techniques that measure the intensities of fluorescent and diffracted X‐rays in a sample simultaneously during irradiation by a high‐energy microfocused incident X‐ray beam. Measured sinograms of the emitted and diffracted intensities were then tomographically reconstructed to generate 2‐D slices of XRF and XRD intensity through the sample, with reconstructed pixel resolution of 1–2 μm, defined by the resolution of the focused incident X‐ray beam. For sample LAP 02342, primary mineral phases that were visualized in reconstructed slices using these techniques included isolated grains of α‐Fe, orthopyroxene, and olivine. For our sample of MAC 88203, XRF/XRD tomography allowed visualization of forsteritic olivine as a primary mineral phase, a vitrified fusion crust at the sample surface, identification of localized Cr‐rich spinels at spatial resolutions of several micrometers, and imaging of a plagioclase‐rich glassy matrix. In the sample of Murchison, major identifiable phases include clinoenstatite‐ and olivine‐rich chondrules, variable serpentine matrix minerals and small Cr‐rich spinels. Most notable in the tomographic analysis of Murchison is the ability to quantitatively distinguish and visualize the complex mixture of serpentine‐group minerals and associated tochilinite–cronstedtite intergrowths. These methods provide new opportunities for spatially resolved characterization of sample texture, mineralogy, crystal structure, and chemical state in unsectioned samples. This provides researchers an ability to characterize such samples internally with minimal disruption of sample micro‐structures and chemistry, possibly without the need for sample extraction from some types of sampling and capture media.
Geochemistry & Geophysics↗