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At least 1,369 records · Page 76

Compression of tokamak boundary plasma simulation data using a maximum volume algorithm for matrix skeleton decomposition

This report demonstrates satisfactory data compression of SOLPS-ITER simulation output ranging from 2D fields, 1D profiles, and 0D scalar variables with a novel matrix decomposition approach. The singular value decomposition (SVD) scales poorly for large matrix sizes and is unsuited to the application on high dimensional data common to fusion plasma physics simulation. In this work, we employ the columns-submatrix-rows (CUR) matrix factorization technique in order to compute a low-rank approximation up to two orders of magnitude faster than the SVD, but within a nominal L2-norm relative error of ε = 10 –2 . In addition, the CUR approach maintains the original format of the data, in its extracted columns and rows, allowing for interpretable data storage at the original resolution of the simulation. We utilize an iterative algorithm to compute the CUR decomposition of simulation output by maximizing the volume, or linearly independent information content, of a low-rank submatrix contained within the data. Experiments over $\textit{n} × \textit{n}$ randomized test matrices with embedded rank-deficient features show that this maximum volume implementation of CUR matrix approximation has reduced asymptotic computational complexity on the order of n compared to the SVD, which scales approximately as $n^3$. These results show that the CUR technique can be used to effectively select time step snapshots (columns) of over 140 SOLPS-ITER output variables and the associated discretized coordinate timeseries (rows) allowing for reconstruction of the complete simulation dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

TbasCO: trait-based comparative ‘omics identifies ecosystem-level and niche-differentiating adaptations of an engineered microbiome

A grand challenge in microbial ecology is disentangling the traits of individual populations within complex communities. Various cultivation-independent approaches have been used to infer traits based on the presence of marker genes. However, marker genes are not linked to traits with complete fidelity, nor do they capture important attributes, such as the timing of gene expression or coordination among traits. To address this, we present an approach for assessing the trait landscape of microbial communities by statistically defining a trait attribute as a shared transcriptional pattern across multiple organisms. Leveraging the KEGG pathway database as a trait library and the Enhanced Biological Phosphorus Removal (EBPR) model microbial ecosystem, we demonstrate that a majority (65%) of traits present in 10 or more genomes have niche-differentiating expression attributes. For example, while many genomes containing high-affinity phosphorus transporter pstABCS display a canonical attribute (e.g. up-regulation under phosphorus starvation), we identified another attribute shared by many genomes where transcription was highest under high phosphorus conditions. Taken together, we provide a novel framework for unravelling the functional dynamics of uncultivated microorganisms by assigning trait-attributes through genome-resolved time-series metatranscriptomics.

59 BASIC BIOLOGICAL SCIENCES↗

Platinum complexes of a boron-rich diphosphine ligand

Continuing herein, we describe the preparation, characterization, and reactivity of two Pt II bis-hydrocarbyl complexes containing the 1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)ethane (P 2 B Cy 4 ) ligand. These scaffolds are readily accessed from four-fold hydroboration of 1,2-bis(diallylphosphino)ethane Pt II precursors. The electrophilcity of such frameworks is showcased by facile coordination of the strong Lewis base, 4-N,N-dimethylaminopyridine (DMAP). Thermolysis reactions of [Pt(P 2 B Cy 4 )(R) 2 ] (R = CH 3 or Ph) show enhanced (and divergent) reactivity when compared to their “all-alkyl” diphosphine counterparts, implicating involvement of the pendant borane groups. This behaviour is attenuated by protection of these units with DMAP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bunch Shaping in Electron Linear Accelerators

Modern electron linear accelerators are often designed to produce smooth bunch distributions characterized by their macroscopic ensemble-average moments. However, an increasing number of accelerator applications call for finer control over the beam distribution, such as by requiring specific shapes for its projection along one coordinate. Ultimately, the control of the beam distribution at the single-particle level could enable new opportunities in accelerator science. This review discusses the recent progress toward controlling electron beam distributions on the “mesoscopic” scale with an emphasis on shaping the beam or introducing complex correlations required for some applications. This review emphasizes experimental and theoretical developments of electron-bunch shaping methods based on bounded external electromagnetic fields or via interactions with the self-generated velocity and radiation fields.

Ha, G.↗

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Thompson, David W.↗

Method bacterial endospore quantification using lanthanide dipicolinate luminescence

A lanthanide is combined with a medium to be tested for endospores. The dipicolinic acid released from the endospores binds the lanthanides, which have distinctive emission (i.e., luminescence) spectra, and are detected using photoluminescence. The concentration of spores is determined by preparing a calibration curve generated from photoluminescence spectra of lanthanide complex mixed with spores of a known concentration. A lanthanide complex is used as the analysis reagent, and is comprised of lanthanide ions bound to multidentate ligands that increase the dipicolinic acid binding constant through a cooperative binding effect with respect to lanthanide chloride. The resulting combined effect of increasing the binding constant and eliminating coordinated water and multiple equilibria increase the sensitivity of the endospore assay by an estimated three to four orders of magnitude over prior art of endospore detection based on lanthanide luminescence.

Ponce, Adrian↗

Information Handling is the Problem

This slide presentation reviews the concerns surrounding the automation of information handling. There are two types of decision support software that supports most Space Station Flight Controllers. one is very simple, and the other is very complex. A middle ground is sought. This is the reason for the Human Centered Autonomous and Assistant Systems Testbed (HCAAST) Project. The aim is to study flight controllers at work, and in the bigger picture, with particular attention to how they handle information and how coordination of multiple teams is performed. The focus of the project is on intelligent assistants to assist in handling information for the flight controllers.

Malin, Jane T.↗

Small Satellites for NASA Earth Science

NASA’s Earth Science Division (ESD) seeks to develop a scientific understanding of Earth and its response to natural and human-induced changes. Earth is a system comprised of diverse components interacting in complex ways. Understanding Earth’s atmosphere, surface and interior, oceans and surface water, ice and snow, and life as a single connected system is necessary in order to improve our predictions of climate, weather, and natural hazards. The ESD’s Flight Program consists of a coordinated series of satellite and airborne systems providing long and short-term, global and regional observations. In addition, the Flight Program provides infrastructure for operating these missions, processing their scientific data, and distributing them on a free and open basis to researchers, operational users, and the public. The Flight Program currently has 24 operating Earth observing space missions and instruments. There are 18 more missions and instruments planned for launch over the next five years. These comprise missions recommended by the National Academies 2017 Earth Science Decadal Survey, missions and selected instruments to ensure availability of key climate data sets, operational missions to sustain the land imaging provided by the Landsat system, and small-sized competitively selected orbital and instrument missions of opportunity belonging to the Earth Venture (EV) program. The Earth Science Decadal Survey, released in early 2018, recommended four new Flight Program elements in addition to the above activities that comprise the Program of Record (POR). Small satellites (~500 kg or less) are essential components of these activities. Presently, there is an increasing use of micro and nanosatellites (or CubeSats) in constellations to support NASA ESD’s scientific objectives. These include the Cyclone Global Navigation Satellite System (CYGNSS) for observing tropical cyclone intensification and genesis factors, the Timed-Resolved Observations of Precipitation structure and storm Intensity with a Constellation of Smallsats (TROPICS) mission, and the Polar Radiant Energy in the Far InfraRed Experiment (PREFIRE) CubeSat mission. ESD small satellite initiatives like the Small Satellite Constellation Data Buy and Venture Class Launch Services (VCLS) are also underway. The Earth Science Technology Office’s (ESTO) In-Space Validation of Earth Science Technologies (InVEST) and the Venture Technology program elements have launched seven 3U and 6U CubeSat missions to validate advanced instruments and related technologies. An equivalent number of InVEST and other technology demonstration CubeSats are being prepared for launch in the next year. An overview of plans and current status including topics related to small satellite enabling activities will be presented.

Neeck, Steven P.↗

STEReO AIAA 2021

STEReO brings together several technologies in Unmanned Aircraft Systems (UAS) Traffic Management (UTM), Autonomy, Communications, Human Factors, and Domain Expertise & Tools, aimed at providing scalability and flexibility, as well as operational resiliency to dynamic changes during a disaster event. Some of the concepts STEReO explores are: collaborative tools to ingest remote sensing information and distribute a common mission data set, apply ad-hoc communication networks to facilitate timely information sharing and communication of changes, vehicle-to-vehicle and onboard autonomy technologies ensure the safety and resiliency of operations, and apply NASA’s UAS traffic management system (UTM) as a public safety UAS Service Supplier (USS) to access and coordinate use of the airspace by both manned and unmanned operations. The potential benefits of STEReO include: standardized, cross-platform communication means increased interoperability and ease of cooperation/collaboration, increased situation awareness to assist in earlier detection and decision making, and scalable to size and complexity of environment, operations, and mission objectives. This presentation gives a high-level overview of the STEReO concept, what we have done so far, and a preview of what's to come.

UAS vehicles↗

Cryptate binding energies towards high throughput chelator design: metadynamics ensembles with cluster–continuum solvation

A tiered forcefield/semiempirical/meta-GGA pipeline together with a thermodynamic scheme designed with error cancellation in mind was developed to calculate binding energies of [2.2.2] cryptate complexes of mono- and divalent cations. Stable complexes of Na, K, Rb, Ca, Zn and Pb were generated, revealing consistent cation–N lengths but highly variable cation–O lengths and an amine stacking mechanism potentially augmenting the cation size selectivity. Metadynamics, used for searching the high-dimensional potential energy surface, together with a cluster–continuum model for affordable – yet accurate – solvation modeling, enabled the discovery of more stable geometries than those previously reported. Similar solvation energy curve shapes for lone vs. coordinated ions enabled rapid solvation convergence via the cancellation of errors stemming from finite cluster sizes. In conclusion, an R 2 of 0.850 vs. experimental aqueous binding energies was obtained, validating this scheme as the backbone of a high-throughput workflow for chelator design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Site Diversity and Mechanism of Metal–Exchanged Zeolite Catalyzed Non–Oxidative Propane Dehydrogenation

Metal-exchanged zeolites are well-known propane dehydrogenation (PDH) catalysts; however, the structure of the active species remains unresolved. In this review, existing PDH catalysts are first surveyed, and then the current understanding of metal-exchanged zeolite catalysts is described in detail. The case of Ga/H-ZSM-5 is employed to showcase that advances in the understanding of structure–activity relations are often accompanied by technological or conceptional breakthroughs. The understanding of Ga speciation at PDH conditions has evolved owing to the advent of in situ/operando characterizations and to the realization that the local coordination environment of Ga species afforded by the zeolite support has a decisive impact on the active site structure. In situ/operando quantitative characterization of catalysts, rigorous determination of intrinsic reaction rates, and predictive computational modeling are all significant in identifying the most active structure in these complex systems. The reaction mechanism could be both intricately related to and nearly independent of the details of the assumed active structure, as in the two main proposed PDH mechanisms on Ga/H-ZSM-5, that is, the carbenium mechanism and the alkyl mechanism. Perspectives on potential approaches to further elucidate the active structure of metal-exchanged zeolite catalysts and reaction mechanisms are discussed in the final section.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conservative discontinuous Galerkin interpolation: Sheared boundary conditions

Local studies of accretion disks and laboratory magnetized plasmas employ analytical coordinate mappings that introduce sheared boundary conditions (BCs). Here, we present a discontinuous Galerkin (DG) algorithm to apply such BCs based on projections and quadrature-free integration. The procedure is high-order accurate, preserves moments exactly and works in multiple dimensions. Tests of increasing complexity are provided, beginning with translations of one and two dimensional fields, followed by 3D and 5D simulations with sheared (twist-shift) BCs. Results show that the algorithm is (p + 1)-order accurate in the DG representation and (p + 2) -order accurate in the cell averages, with p being the order of the polynomial basis. Quantification of the algorithm's hyperdiffusion and discussion of aliasing errors are given. This technique enables conservative local simulations of plasma turbulence with DG, not possible until now.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Heterogenization of Homogeneous Ruthenium(II) Catalysts for Carbon-Neutral Dehydrogenation of Polyalcohols

Liquid organic hydrogen carrier (LOHC) systems are an excellent alternative to pressurized gas and liquid hydrogen storage technologies due to their high volumetric storage capacities and straightforward adaptation to existing infrastructure. Homogeneous catalysts are promising for the selective and reversible release of hydrogen from LOHC. However, separation from product mixtures and recycling inhibit their use, particularly when comprised of costly low-abundance elements, motivating the development of heterogeneous versions that are more easily recovered and reused. Here, we describe two methods for the heterogenization of molecular Ru catalysts that efficiently dehydrogenate the polyalcohol LOHCs ethylene glycol (EG) and 1,2-propanediol (1,2-PDO). The heterogeneous versions of these catalysts maintain catalytic activity for hydrogen production comparable to the homogeneous complexes, with up to 81% conversion and 99% selectivity. Further, DFT modeling indicates mechanistic similarities for the dehydrogenations of EG and 1,2-PDO, with the rate-limiting steps associated with protonation of the Ru–H bond to form H 2 and the alkoxide species coordinated to Ru(II), followed by β-hydride elimination to regenerate the Ru–H bond. Overall, the data suggest these heterogenized molecular catalysts have potential for practical use in polyalcohol-based LOHC systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of Capping Agents in the Synthesis of Salicylate-Capped Zinc Oxide Nanoparticles

Capping agents are often used for controlling the size, aggregation, and properties of nanoparticles. To guide the design of improved nanomaterials for targeted performance, one can use mechanistic insights into the interactions between capping agents and nanoparticles. Here, we employ density functional theory (DFT), reactive force-field molecular dynamics (ReaxFF MD) simulations, and optical spectroscopy to study the interactions between salicylate, as a model capping agent, and zinc oxide (ZnO) nanoparticles. In this work, we find that salicylate strongly interacts with the nanoparticle via the formation of O–Zn bonds in a distorted six-membered coordination ring structure. We describe the mechanisms of capping of ZnO nanoparticles by salicylate via three different binding modes. Simulations indicate that salicylate undergoes dissociative adsorption at the highly active surface Zn sites via a hydrogen-transfer process, thereby forming a tridentate configuration. The water-mediated interaction also facilitates the dissociative adsorption, leading to two salicylate O atoms coordinating with a surface Zn atom, while the other salicylate O atom bonds with another surface Zn atom. For molecular adsorption, binding free energies indicate that salicylate binds more strongly to ZnO, often in a bidentate configuration, than water does. The formation of the salicylate–ZnO complex is substantiated by UV–visible and Fourier transform infrared spectra. We find that the C=O stretching mode of salicylate becomes softened when it interacts with the nanoparticle, suggesting chemisorption of salicylate on ZnO. Although DFT predicts strong interaction between salicylate and ZnO, ReaxFF MD simulation indicates the moderate interaction between these two components in aqueous solution. Water molecules in close contact with the nanoparticle surface undergo dissociation, thus resulting in a surface hydroxyl, a reactive oxygen species that may influence the nanoparticle’s catalytic properties. Overall, the atomic-level information provided here can guide the selection process of salicylate as an appropriate agent for ZnO nanoparticle synthesis when strong interactions of particles with capping agents are required.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of High-Spin Species and Pendant Amines in Electrocatalytic Alcohol Oxidation by a Nickel Phosphine Complex

We report the development of active and efficient electrocatalysts for oxidation of alcohols using earth-abundant metals will aid the progress towards a renewable energy economy. Here we present a detailed mechanistic study of electrocatalytic benzyl alcohol oxidation by a molecular nickel complex containing pendant amines using a combination of kinetic studies, NMR spectroscopy, and density functional theory. The catalyst preferentially binds alcohol in high-spin octahedral geometry, but this complex is not readily deprotonated by exogeneous base and inhibits catalysis. Dissociation of one or more solvent ligands returns the complex to a low-spin state that can be deprotonated. Kinetic modeling indicates the off-cycle high-spin intermediate lowers the catalytic turnover frequency by a factor of eight, suggesting that substantial gains in activity can be attained by improvements to the catalyst coordination geometry. In a second finding, we demonstrate the pendant amine of the catalyst only functions as a proton relay for the potential-determining step, oxidation of a nickel hydride intermediate, but does not have a substantial impact on the overall rate for oxidation of benzyl alcohol to benzaldehyde. This result contradicts the common expectation for pendant amines to participate in rate-limiting proton transfer reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin–vibronic coherence drives singlet–triplet conversion

Design-specific control over the transitions between excited electronic states with different spin multiplicities is of the utmost importance in molecular and materials chemistry. Previous studies have indicated that the combination of spin-orbit and vibronic effects, collectively termed the spin-vibronic effect, can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings. However, it has been difficult to identify precise experimental manifestations of the spin-vibronic mechanism. Here we present coherence spectroscopy experiments that reveal the interplay between the spin, electronic and vibrational degrees of freedom that drive efficient singlet-triplet conversion in four structurally related dinuclear Pt(II) metal-metal-to-ligand charge-transfer (MMLCT) complexes. Photoexcitation activates the formation of a Pt-Pt bond, launching a stretching vibrational wavepacket. The molecular-structure-dependent decoherence and recoherence dynamics of this wavepacket resolve the spin-vibronic mechanism. Further, we find that vectorial motion along the Pt-Pt stretching coordinates tunes the singlet and intermediate-state energy gap irreversibly towards the conical intersection and subsequently drives formation of the lowest stable triplet state in a ratcheting fashion. This work demonstrates the viability of using vibronic coherences as probes to clarify the interplay among spin, electronic and nuclear dynamics in spin-conversion processes, and this could inspire new modular designs to tailor the properties of excited states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accurate prediction of global-density-dependent range-separation parameters based on machine learning

In this work, we develop an accurate and efficient XGBoost machine learning model for predicting the global-density-dependent range-separation parameter, ωGDD, for long-range corrected functional (LRC)-ωPBE. This ωGDDML model has been built using a wide range of systems (11 466 complexes, ten different elements, and up to 139 heavy atoms) with fingerprints for the local atomic environment and histograms of distances for the long-range atomic correlation for mapping the quantum mechanical range-separation values. The promising performance on the testing set with 7046 complexes shows a mean absolute error of 0.001 117 a0−1 and only five systems (0.07%) with an absolute error larger than 0.01 a0−1, which indicates the good transferability of our ωGDDML model. In addition, the only required input to obtain ωGDDML is the Cartesian coordinates without electronic structure calculations, thereby enabling rapid predictions. LRC-ωPBE(ωGDDML) is used to predict polarizabilities for a series of oligomers, where polarizabilities are sensitive to the asymptotic density decay and are crucial in a variety of applications, including the calculations of dispersion corrections and refractive index, and surpasses the performance of all other popular density functionals except for the non-tuned LRC-ωPBE. Finally, LRC-ωPBE (ωGDDML) combined with (extended) symmetry-adapted perturbation theory is used in calculating noncovalent interactions to further show that the traditional ab initio system-specific tuning procedure can be bypassed. The present study not only provides an accurate and efficient way to determine the range-separation parameter for LRC-ωPBE but also shows the synergistic benefits of fusing the power of physically inspired density functional LRC-ωPBE and the data-driven ωGDDML model.

Chemistry↗

Spectral broadening and vibronic dynamics of the S2 state of canthaxanthin in the orange carotenoid protein

We have performed a series of broadband multidimensional electronic spectroscopy experiments to probe the electronic and vibrational dynamics of the canthaxanthin chromophore of the Orange Carotenoid Protein (OCP) from Synechocystis sp. PCC 6803 in its photoactivated red state, OCPR. Cross-peaks observed below the diagonal of the two-dimensional electronic spectrum indicate that absorption transitions prepare the bright S2 state of the ketocarotenoid canthaxanthin near to a sequence of conical intersections, allowing passage to the dark S1 state via the Sx intermediate in <50 fs. Rapid damping of excited-state coherent wavepacket motions suggests that the branching coordinates of the conical intersections include out-of-plane deformation and C=C stretching coordinates of the π-conjugated isoprenoid backbone. The unusual proximity of the Franck–Condon S2 state structure to the conical intersections with Sx and S1 suggests that the protein surroundings of canthaxanthin prepare it to function as an excitation energy trap in the OCPR–phycobilisome complex. Numerical simulations using the multimode Brownian oscillator model demonstrate that the ground-state absorption spectrum of OCPR overlaps with the fluorescence emission spectrum of allophycocyanin due to spectral broadening derived especially from the intramolecular motions of the canthaxanthin chromophore in its binding site.

Yang, Kunwei↗