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At least 631 records · Page 35

Unsupervised atomic data mining via multi-kernel graph autoencoders for machine learning force fields

Constructing a chemically diverse dataset while avoiding sampling bias is critical to training efficient and generalizable force fields. However, in computational chemistry and materials science, many common dataset generation techniques are prone to oversampling regions of the potential energy surface. Furthermore, these regions can be difficult to identify and isolate from each other or may not align well with human intuition, making it challenging to systematically remove bias in the dataset. While traditional clustering and pruning (down-sampling) approaches can be useful for this, they can often lead to information loss or a failure to properly identify distinct regions of the potential energy surface due to difficulties associated with the high dimensionality of atomic descriptors. In this work, we introduce the Multi-kernel Edge Attention-based Graph Autoencoder (MEAGraph) model, an unsupervised approach for analyzing atomic datasets. MEAGraph combines multiple linear kernel transformations with attention-based message passing to capture geometric sensitivity and enable effective dataset pruning without relying on labels or extensive training. Demonstrated applications on niobium, tantalum, and iron datasets show that MEAGraph efficiently groups similar atomic environments, allowing for the use of basic pruning techniques for removing sampling bias. This approach provides an effective method for representation learning and clustering that can be used for data analysis, outlier detection, and dataset optimization.

Materials science↗

Ecological and genomic analyses of candidate phylum WPS-2 bacteria in an unvegetated soil

Members of the bacterial candidate phylum WPS-2 (or Eremiobacterota) are abundant in several dry, bare soil environments. In a bare soil deposited by an extinct iron-sulfur spring, we found that WPS-2 comprised up to 24% of the bacterial community and up to 108 cells per g of soil based on 16S rRNA gene sequencing and quantification. A single genus-level cluster (Ca. Rubrimentiphilum) predominated in bare soils but was less abundant in adjacent forest. Nearly complete genomes of Ca. Rubrimentiphilum were recovered as single amplified genomes (SAGs) and metagenome-assembled genomes (MAGs). Surprisingly, given the abundance of WPS-2 in bare soils, the genomes did not indicate any capacity for autotrophy, phototrophy, or trace gas metabolism. Instead, they suggest a predominantly aerobic organoheterotrophic lifestyle, perhaps based on scavenging amino acids, nucleotides, and complex oligopeptides, along with lithotrophic capacity on thiosulfate. Network analyses of the entire community showed that some species of Chloroflexi, Actinobacteria, and candidate phylum AD3 (or Dormibacterota) co-occurred with Ca. Rubrimentiphilum and may represent ecological or metabolic partners. We propose that Ca. Rubrimentiphilum act as efficient heterotrophic scavengers. Combined with previous studies, these data suggest that the phylum WPS-2 includes bacteria with diverse metabolic capabilities.

59 BASIC BIOLOGICAL SCIENCES↗

Charon User Manual (V.2.1) (Rev.01)

This manual gives usage information for the Charon semiconductor device simulator. Charon was developed to meet the modeling needs of Sandia National Laboratories and to improve on the capabilities of the commercial TCAD simulators; in particular, the additional capabilities are running very large simulations on parallel computers and modeling displacement damage and other radiation effects in significant detail. The parallel capabilities are based around the MPI interface which allows the code to be ported to a large number of parallel systems, including linux clusters and proprietary "big iron" systems found at the national laboratories and in large industrial settings.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Charon User Manual: v. 2.2 (revision1)

This manual gives usage information for the Charon semiconductor device simulator. Charon was developed to meet the modeling needs of Sandia National Laboratories and to improve on the capabilities of the commercial TCAD simulators; in particular, the additional capabilities are running very large simulations on parallel computers and modeling displacement damage and other radiation effects in significant detail. The parallel capabilities are based around the MPI interface which allows the code to be ported to a large number of parallel systems, including linux clusters and proprietary “big iron” systems found at the national laboratories and in large industrial settings.

42 ENGINEERING↗

Low-cost, portable optical sensors for critical mineral prospecting and process monitoring

A combination of projected demand increases for economically critical minerals and a monopolistic global marketplace for these minerals has caused concern over supply chain vulnerabilities, which would impact energy, national defense, and advanced technology production. Domestic production of critical minerals is hindered by expensive and non-portable methods for analyzing metal concentration, which is vital both for resource prospecting and process monitoring. Here, a suite of luminescent materials along with portable instrumentation is presented for fluorescence-based detection of trace concentrations of critical minerals (cobalt, rare earth elements, and aluminum) as well as common gangue metals that are removed during processing (iron and aluminum). A metal-organic framework comprised of zinc, adenine, and trimesic acid immobilized on a fiber optic tip is capable of sensing part-per-billion concentrations of terbium, europium, dysprosium, and samarium through a sensitization approach, in which individual elements produce characteristic emission bands enabling multiple rare earths to be simultaneously detected and distinguished. A deep-UV light emitting diode is used as the excitation source, while a portable spectrometer is used to detect the emitted light. A similar optical set-up is coupled with two different carbon dot materials, which can detect low part-per-million concentrations of cobalt and iron in acidic environments. Metal-organic framework thin films comprised of copper and 2-aminoterephthalic acid are used in tandem with a portable optical set-up to further detect aluminum, with successful deployment in real fly ash leachates. Taken together, these technologies provide an inexpensive and sensitive path towards characterizing economically critical metals.

characterization and extraction of rare earth elem↗

Soil properties and root characteristics across four lowland Panamanian forests from 0 - 1 m soil depths

Objectives:Fine roots significantly influence ecosystem-scale cycling of nutrients, carbon (C), and water, yet there is limited understanding of how fine root traits vary across and within tropical forests, some of Earth's most C-rich ecosystems. The biomass of fine roots can impact soil carbon storage, as root mortality is a primary source of new carbon to soils. A positive relationship has been observed between fine root biomass and soil carbon stocks in Panama (Cusack et al 2018). Beyond biomass, root characteristics like specific root length (SRL) could also influence soil carbon, as roots with higher SRL are less dense and thinner, potentially decomposing more easily or promoting soil aggregation. Understanding the effects of root morphology and tissue quality on soil carbon storage and with soil properties in general can improve predictions of landscape-scale carbon patterns. We aggregated new data of root biomass, morphology and nutrient content at 0-10 cm, 10-20 cm, 20-50 cm and 50-100 cm depth increments across four distinct lowland Panamanian forests and paired with already published datasets (Cusack et al 2018; Cusack and Turner 2020) of soil chemistry from the same sites and soil depths to explore relationship between soil carbon stocks and root characteristics.Datasets included:The datasets provided include .csv and .xlsx files for fine root characteristics and soil chemistry from four different forests across 0-10 cm, 10-20 cm, 20-50 cm, and 50-100 cm depth increments. Root characteristics include live fine root biomass, dead fine root biomass, coarse root biomass, specific root length, root diameter, root tissue density, specific root area, root %N, root %C, and root C/N ratio. Soil chemistry data includes total carbon (TC), dissolved organic carbon (DOC), bulk density, total phosphorus (TP), available phosphorus (AEM Pi), and various Mehlich-extractable elements such as aluminum, calcium, iron, potassium, manganese, phosphorus, and zinc. Nitrogen content measures include ammonium, nitrate, total dissolved nitrogen (TDN), dissolved inorganic nitrogen (DIN), and dissolved organic nitrogen (DON). The dataset also includes total exchangeable bases (TEB) and effective cation exchange capacity (ECEC) in both centimoles of charge per kilogram and micromoles of charge per gram. The soil chemistry data was obtained from Cusack et al (2018) and Cusack and Turner (2020) and paired with root characteristics data for the same depth increments and sites. Additionally, a .kml file is provided with coordinates for all 32 plots included in the study across four forests (n = 8 plots per site). Root data was averaged across these 8 plots per site and soil data was collected in one pit in each site. This dataset serves as baseline data before a throughfall exclusion experiment, Panama Rainforest Changes with Experimental Drying (PARCHED), was implemented. No special software is needed to open these files.

54 ENVIRONMENTAL SCIENCES↗

Iron( IV ) alkyl complexes: electronic structure contributions to Fe–C bond homolysis and migration reactions that form N–C bonds from N 2

High-valent iron alkyl complexes are rare, as they are prone to Fe–C bond homolysis. Here, we describe an unusual way to access formally iron(IV) alkyl complexes through double silylation of iron(I) alkyl dinitrogen complexes to form an NNSi 2 group. Spectroscopically validated computations show that the disilylehydrazido(2−) ligand stabilizes the formal iron(IV) oxidation state through a strongly covalent Fe–N π-interaction, in which one π-bond fits an “inverted field” description. This means that the two bonding electrons are localized more on the metal than the ligand, and thus an iron(II) resonance structure is a significant contributor, similar to the previously-reported phenyl analogue. However, in contrast to the phenyl complex which has an S = 1 ground state, the ground state of the alkyl complex is S = 2, which places one electron in the π* orbital, leading to longer and weaker Fe–N bonds. The reactivity of these hydrazido(2−) complexes is dependent on the steric and electronic properties of the specific alkyl group. When the alkyl group is the bulky trimethylsilylmethyl, the formally iron(IV) species is stable at room temperature and no migration of the alkyl ligand is observed. However, the analogous complex with the smaller methyl ligand does indeed undergo migration of the carbon-based ligand to the NNSi 2 group to form a new N–C bond. This migration is followed by isomerization of the hydrazido ligand, and the product exists as two isomers that have distinct η 1 and η 2 binding of the hydrazido group. Lastly, when the alkyl group is benzyl, the Fe–C bond homolyzes to give a three-coordinate hydrazido(2−) complex which is likely due to the greater stability of a benzyl radical compared to that for methyl or trimethylsilylmethyl. These studies demonstrate the availability of a hydrocarbyl migration pathway at formally iron(IV) centers to form new N–C bonds directly to N 2 , though product selectivity is highly dependent on the identity of the migrating group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Material extrusion with integrated compression molding of NdFeB/SmFeN nylon bonded magnets using small- and large-scale pellet-based 3D-printers

High-density bonded rare-earth magnets are manufactured using pellet-fed additive manufacturing (AM)/material extrusion and an integrated additive manufacturing-compression molding (AM-CM) process. Neodymium iron boron – samarium iron nitride in polyamide 12 (NdFeB-SmFeN/PA12) of 93 % weight fraction (65 % volume fraction) are used for the study. The mechanical properties (tensile strength and modulus), magnetic properties (maximum energy density, coercivity, remanence) are reported. Manufacturing parameters such as layer height, barrel temperatures, screw speed and gantry feed rate are optimized to obtain the highest possible density of the magnets using a small-scale desktop material extrusion printer. Large scale integrated additive manufacturing-compression molding (AM-CM) is then utilized to increase the density of the magnets by reducing porosity defects common in the material extrusion process. The density of as-printed magnets was 5.2 g/cm 3 with a BH max value of 124.14 kJ/m 3 , tensile strength of 20 MPa and a modulus of 2 GPa. AM-CM increased the density of the compound by 5.5 % (5.49 g/cm 3 ). The reduction in porosity was confirmed using X-ray tomography (XCT). Improvement in mechanical strength of the material was also observed, with an increase in tensile strength of 25 % (25.09 MPa) and increase in tensile modulus of 275 % (5.49 GPa). Scanning electron microscopy showed increased particle-matrix adhesion with the integrated AM-CM process.

36 MATERIALS SCIENCE↗

Atomic Layer Deposition for Spatial Control of Redox Reaction Selectivity

Photocatalytic water splitting holds great potential in the pursuit of the U.S. Department of Energy's Hydrogen Shot initiative to bring the cost of H2 to $1/kg by 2031. A key challenge in the development of photocatalysts is increasing their overall solar-to-hydrogen efficiency by enhancing charge separation yields and redox selectivity. In this work, we use area selective ALD of oxide films to develop tunable interphase layers for selective oxidation and reduction reactions on a single substrate. This presentation details initial synthesis and characterization of Pt- and Au-based planar thin film electrodes in which Au regions were deactivated towards ALD growth through self-assembled thiol monolayers. The suppression of TiO2 ALD selectivity of thiols was assessed through ellipsometry, X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. A patterned planar sample comprised of interdigitated arrays of Au and Pt, used as a surrogate for a photocatalyst particle containing two different co-catalysts, was exposed to ALD growth and removal of the inhibitor species. Scanning electrochemical microscopy (SECM) was used then to probe the local activity of different regions of the patterned surface towards the hydrogen evolution reaction (HER) and iron oxidation and correlated with the ionic and e- blocking effects of the area selective ALD coating. We will also detail the application of these findings to the ongoing development of 3D, particle-based photocatalysts.

atomic layer deposition↗

In Situ Identification of Reaction Intermediates and Mechanistic Understandings of Methane Oxidation over Hematite: A Combined Experimental and Theoretical Study

Effective methane utilization for either clean power generation or value-added chemical production has been a subject of growing attention worldwide for decades, yet challenges persist mostly in relation to methane activation under mild conditions. Here, we report hematite, an earth-abundant material, to be highly effective and thermally stable to catalyze methane combustion at low temperatures (<500 °C) with a low light-off temperature of 230 °C and 100% selectivity to CO 2 . The reported performance is impressive and comparable to those of precious-metal-based catalysts, with a low apparent activation energy of 17.60 kcal·mol –1 . Our theoretical analysis shows that the excellent performance stems from a tetra-iron center with an antiferromagnetically coupled iron dimer on the hematite (110) surface, analogous to that of the methanotroph enzyme methane monooxygenase that activates methane at ambient conditions in nature. Isotopic oxygen tracer experiments support a Mars van Krevelen redox mechanism where CH 4 is activated by reaction with a hematite surface oxygen first, followed by a catalytic cycle through a molecular-dioxygen-assisted pathway. Surface studies with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations reveal the evolution of reaction intermediates from a methoxy CH 3 –O–Fe, to a bridging bidentate formate b-HCOO–Fe, to a monodentate formate m-HCOO–Fe, before CO 2 is eventually formed via a combination of thermal hydrogen-atom transfer (HAT) and proton-coupled electron transfer (PCET) processes. Finally, the elucidation of the reaction mechanism and the intermediate evolutionary profile may allow future development of catalytic syntheses of oxygenated products from CH 4 in gas-phase heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A comprehensive final summary of the MCNP calculations performed concerning the UW 137 Cs release event

This document combines and supersedes earlier reports (e.g. LA-UR-19-32358 and LA-UR-20- 22216) that discussed MCNP-calculated conversion factors (count rate per unit activity per unit area) for collimated 2”x2” NaI detectors (Ludlum model 44-10 and Thermo model SPA3) in contact with various surfaces of interest to the University of Washington 137 Cs release event. These surfaces include: Exterior surface of round and rectangular ducts, Exterior surface of outdoor brick work, Exterior surface of cast iron pipes, Exterior surface of an O 2 filter assembly For each surface, the calculated conversion factors allowed inferences on 137 Cs activity on interior surfaces based on exterior contact measurements of the 662 keV photopeak count rate. The MCNP calculations included the effect of attached collimators (i.e. either a Pb/Sb-based Ludlum or a W-based “Rees” model) on detector response. As a consequence, the conversion factors only apply to the appropriate collimated 2”x2” NaI detector operated in pulse height analysis (PHA) mode. Other assumptions affecting the calculations and valid application of the conversion factors will be outlined below.

54 ENVIRONMENTAL SCIENCES↗

Signal Differentiation of Moving Magnetic Nanoparticles for Enhanced Biodetection and Diagnostics

Magnetic nanoparticles are extensively utilized as markers/signal labelling in various biomedical applications. Detecting and distinguishing magnetic signals from similarly sized moving magnetic nanoparticles in microfluidic systems is crucial yet challenging for biosensing. In this study, we have developed an original method to detect and differentiate magnetic signals from moving superparamagnetic (SPM) and ferrimagnetic (FM) nanoparticles of comparable sizes. Our approach utilizes a highly sensitive magnetic-coil-based sensor that harnesses the combined effects of giant magnetoimpedance (GMI) and an LC-resonance circuit, offering performance superior to that of conventional GMI sensors. Iron oxide nanoparticles, which have similar particle sizes but differing coercivities (zero for SPM and non-zero for FM) or similar zero coercivities but differing particle sizes, flow through the magnetic coil at controlled velocities. Their distinct effects are analyzed through changes in the complex impedance of the sensing system. Our findings provide a unique pathway for utilizing SPM and FM nanoparticles as innovative magnetic markers to identify specific biological entities, thereby expanding their potential applications.

Hwang, Kee Young↗

Portable Luminescent Sensor Technologies for Economically Critical Metals

Presentation on the development of sensing materials and compact platforms for the photoluminescence-based detection of economically critical metals, including rare earth elements, cobalt, and aluminum. The important of detecting metals that interfere with critical metal processing, such as iron and aluminum, are also discussed. The presented results represent a significant step forward in reducing the economic and time costs associated with the characterization of metals during prospecting and downstream processing.

Crawford, Scott↗

Electron Bifurcating Hydrogenases

The importance of electron-bifurcating enzymes is manifest by their ability to maximize energy efficiency. Specifically, they couple a downhill oxidation-reduction (redox) reaction with an uphill redox reaction. Since the rapid increase in the discovery of bifurcating enzymes starting in 2008, there has been interest in incorporating their mechanistic principles into artificial/semiartificial systems to drive chemically challenging reactions. This has yet to be achieved, partly because the details of electron bifurcation, i.e. mechanisms, are largely elusive. Nevertheless, much progress has been made in understanding reactivities, structures, and some mechanistic aspects of these enzymes. Notable examples are electron-bifurcating hydrogenases, which are the focus of this chapter. The chapter is organized as follows. Section 11.1 provides an overview of hydrogenases and electron bifurcation. In Section 11.2, some physiological roles of electron-bifurcating hydrogenases are highlighted. Additionally, electron-bifurcating subunit compositions and biochemical reactivities are comprehensively tabulated, and some key points/considerations about these are noted. In Section 11.3, we discuss the known structures of these enzymes, which provide insight into their complex arrangements of redox cofactors, such as iron-sulfur clusters. Also provided are tabulations and discussions of some biophysical properties of the cofactors. In Section 11.4, we discuss the mechanistic proposals of these enzymes, which are primarily based on structural information. Areas of research that are much needed are outlined in Section 11.5. We conclude on the note that what is learned from electron-bifurcating hydrogenases has applicability to other bifurcating enzymes, nonbifurcating analogs, and mechanistic enzymology at large.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantification of Swelling in Hematite Pellets Reduced Using Hydrogen–Nitrogen Gas Mixture

Iron ore pellets are reduced in a 50%H 2 –50%N 2 1 atm gas mixture at 750, 800, 850, 900, and 950 °C while simultaneously documenting swelling (change in pellet radius) and weight change. Swelling increases with increasing temperature, with catastrophic swelling (>20% of reduction swelling index) observed at 850, 900, and 950 °C. As the pellet is reduced, the pellet radius increases until 40–50% reduction is achieved, followed by a decrease in diameter beyond 40–50% reduction at 750 and 850 °C. At 950 °C, the pellet radius continues to increase with additional pellet reduction without any subsequent decrease in diameter. Scanning electron microscopy (SEM) analysis shows that the neighboring grains inside the pellet sinter together at 750 and 850 °C, whereas the individual grains sinter internally at 950 °C. SEM analysis and observations suggest that the reduction process at 750 and 850 °C can be approximated as a topochemical reaction process, while the reduction process at 950 °C can no longer be approximated as a topochemical reaction process. In conclusion, an empirical equation for the radius of the pellet is derived with fitting parameters dependent on temperature and the degree of reduction of the pellet undergoing reduction based on the experimental data.

08 HYDROGEN↗

Annotation of DOM metabolomes with an ultrahigh resolution mass spectrometry molecular formula library

Current approaches to analyzing metabolomic data often rely on matching MS/MS fragmentation data to sparse libraries or databases. This approach results in limited identification of features, often with less than 10% of the dataset being annotated. A complementary approach is to assign molecular formula to features based on accurate mass measurements, but the platforms commonly used for metabolomics do not have the needed accuracy or resolving power to do this robustly, particularly for larger molecules. Using our newly modified analysis tool, CoreMS, we generated a library of molecular formula from pooled samples analyzed with LC-21T FT-ICR MS. This library successfully annotated approximately 53.2% of features identified from the exometabolome of marine diatom Phaeodactylum tricornutum – a nearly ten-fold increase over the 5.9% annotation rate achieved using a conventional MS/MS library matching approach. Using this FT-ICR MS library approach, we were able to differentiate differences in the exometabolome of P. tricornutum in iron replete and iron limited conditions, with 668 metabolites being differentially expressed (p < 0.05, 2 x intensity difference) under these conditions. The traditional MS/MS fragmentation-based annotation approach only annotated 61 of these metabolites, while our novel pipeline annotated 450 metabolites and revealed 12 metabolites that were significantly more abundant under low iron conditions. Our results demonstrate the utility of ultrahigh resolution mass spectrometry for generating more comprehensive and confident molecular annotations.

21T-FTICR-MS, CoreMS↗

Understanding Reaction Networks through Controlled Approach to Equilibrium Experiments Using Transient Methods

We report a combined experimental/theoretical approach to studying heterogeneous gas/solid catalytic processes using low-pressure pulse response experiments achieving a controlled approach to equilibrium that combined with quantum mechanics (QM)-based computational analysis provides information needed to reconstruct the role of the different surface reaction steps. We demonstrate this approach using model catalysts for ammonia synthesis/decomposition. Polycrystalline iron and cobalt are studied via low-pressure TAP (temporal analysis of products) pulse response, with the results interpreted through reaction free energies calculated using QM on Fe-BCC(110), Fe-BCC(111), and Co-FCC(111) facets. In TAP experiments, simultaneous pulsing of ammonia and deuterium creates a condition where the participation of reactants and products can be distinguished in both forward and reverse reaction steps. This establishes a balance between competitive reactions for D* surface species that is used to observe the influence of steps leading to nitrogen formation as the nitrogen product remains far from equilibrium. Here, the approach to equilibrium is further controlled by introducing delay timing between NH 3 and D 2 which allows time for surface reactions to evolve before being driven in the reverse direction from the gas phase. The resulting isotopic product distributions for NH 2 D, NHD 2 , and HD at different temperatures and delay times and NH 3 /D 2 pulsing order reveal the role of the N 2 formation barrier in controlling the surface concentration of NH x * species, as well as providing information on the surface lifetimes of key reaction intermediates. Conclusions derived for monometallic materials are used to interpret experimental results on a more complex and active CoFe bimetallic catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and density of silicon carbide to 1.5 TPa and implications for extrasolar planets

There has been considerable recent interest in the high-pressure behavior of silicon carbide, a potential major constituent of carbon-rich exoplanets. In this work, the atomic-level structure of SiC was determined through in situ X-ray diffraction under laser-driven ramp compression up to 1.5 TPa; stresses more than seven times greater than previous static and shock data. Here we show that the B1-type structure persists over this stress range and we have constrained its equation of state (EOS). Using this data we have determined the first experimentally based mass-radius curves for a hypothetical pure SiC planet. Interior structure models are constructed for planets consisting of a SiC-rich mantle and iron-rich core. Carbide planets are found to be ~10% less dense than corresponding terrestrial planets.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗