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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
NASA NTRS2008

The Young Massive Stellar Cluster Sandage-96 after the Explosion of SN 2004DJ in NGC 2403

The bright supernova 2004dj occurred within the young massive stellar cluster Sandage-96 in a spiral arm of NGC 2403, close to other star-forming complexes. New multi-wavelength observations obtained with several ground-based- and space telescopes are combined to study the radiation from Sandage-96 after SN 2004dj faded away. The late-time light curves show that Sandage-96 started to dominate the flux in the optical bands after September, 2006 (+800 days after explosion). The optical fluxes are equal to the pre-explosion ones, suggesting that Sandage-96 has survived the explosion without significant changes in its stellar population. An optical Keck-spectrum obtained at +900 days after explosion shows the dominant blue continuum from the cluster stars shortward of 6000 A as well as strong SN nebular emission lines redward. The integrated SED of the cluster has been extended into the UV-region by archival XMM-Newton and new Swift observations, and compared with theoretical models. The outer parts of the cluster have been resolved by HST allowing the construction of a color-magnitude diagram. The fitting of the cluster SED with theoretical isochrones results in two possible solutions with ages being 9+/-1 Myr and 30+/-10 Myr, depending on the assumed metallicity and the theoretical model family. The isochrone fitting of the color-magnitude diagram indicates that the outer part of the cluster consists of stars having an age dispersion of 16 < t < 63 Myr, which is similar to that of nearby field stars. This age discrepancy may be resolved by the hypothesis that the outskirt of Sandage-96 is contaminated by stars captured from the field during cluster formation. The young age of Sandage-96 and the comparison of its pre- and post-explosion SEDs suggest a progenitor mass of 15 < or equal to M(sub prog) < 25 Stellar Mass.

Vinko, J.↗
DOE OSTI2025

Single-Walled Carbon Nanotubes with Confined Chalcogens as the Catalysts and Electrodes for Oxygen Reduction Reaction in Fuel Cells

The goal of this project is to synthesize and characterize a new non-metal electro-catalyst for oxygen reduction reaction (ORR) for fuel cell applications. The intended catalyst is a composite material composed of sulfur chains encapsulated in narrow diameter single-walled carbon nanotubes (S@SWNTs). S@SWNTs were successfully synthesized through sulfur vapor infusion method, and validated with Raman spectroscopy. However, the electrochemical analysis on the ORR catalytic activity of S@SWNTs indicated that it had low ORR catalytic activity. Our theoretical study based on density functional theory (DFT) revealed that the poor oxygen adsorption (low binding energy) on the surface of S@SWNTs was the bottleneck of the entire catalytic reaction. The focus of the project was subsequently pivoted to the development of a new non-noble metal ORR catalyst that could provide durability in acidic electrolyte. The hypothesis was to encapsulate small iron (Fe) clusters in SWNTs (Fe@SWNTs) can provide ORR electro-catalytic activity and long durability in acidic environment. DFT-based computational studies were carried out to explore the feasibility of the Fe@SWNTs catalyst. The theoretical study indicated that Fe@SWNTs indeed could catalyze the ORR with lower theoretical overpotential than platinum (Pt). However, its weaker bonding energy with oxygen was the bottleneck of the overall reaction. On the other hand, Fe clusters (composed of 7 Fe atoms) encapsulated in nitrogen-doped SWNTs (Fe 7 @N 4 WSNTs) showed proper oxygen adsorption by the Fe cluster and low theoretical overpotential of ORR. Comparing to the Fe single atom catalyst on N-doped SWNTs (Fe-N 4 SWNTs), which is one the best non-noble metal ORR catalysts reported in the literature, the Fe 7 @N 4 WSNTs showed lower overpotential and better resistance to acidic environment. Fe encapsulated N-doped SWNTs were synthesized with ferrocene as the Fe precursors through vapor infusion method, and experimental validate is underway. This study theoretically demonstrated the feasibility of a new type of non-noble metal electro-catalyst for ORR that could have high catalytic activity and long durability.

08 HYDROGEN↗
DOE OSTI2023

Exploring the stellar populations of backsplash galaxies

Backsplash galaxies are those that traverse and overshoot cluster cores as they fall into these structures. They are affected by environment, and should stand out in contrast to the infalling population. We target galaxies in the vicinity of clusters (R≳R 200 ) and select a sample in projected phase space (PPS), from the compilation of Sampaio et al. based on SDSS data. We present a statistical analysis, comparing two regions in PPS, with the same projected distance to the cluster but different velocity. The analysis relies on the presence of variations in the stellar population content of backsplash galaxies. We find a lower limit in the fractional contribution of ∼5 per cent with respect to the general sample of infalling galaxies at similar group-centric distance when using single line strength analysis, or ∼15-30 per cent when adopting bivariate distributions. The stellar populations show a subtle but significant difference towards older ages, and a higher fraction of quiescent galaxies. We also compare this set with a general field sample, where a substantially larger difference in galaxy properties is found, with the field sample being consistently younger, metal poorer and with a lower fraction of quiescent galaxies. Noting that our ‘cluster’ sample is located outside of the virial radius, we expect this difference to be caused by pre-processing of the infalling galaxies in the overall higher density regions.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1988

Supercomputer chemistry at the University of Minnesota

The focus of cluster chemistry studies at the University of Minnesota is on the adsorption of small hydrocarbon molecules on metal and graphite surfaces, and on the substitution defects in diamond and silicon. Of particular interest is the study of very large systems such as the C60 molecule and the C150H30 molecule. Many of the properties of such clusters converge extremely slowly toward bulk values. Ultrathin films and microporous media are discussed as well as the Brownian dynamics of polymers.

Almlof, Jan↗
NASA NTRS1989

The ages of globular cluster stars - Effects of rotation on pre-main-sequence, main-sequence, and turnoff evolution

Evolutionary sequences for low-metallicity stars (Z ranging from 0.001 to 0.0001) to study the effects of internal stellar rotation on the evolutionary time scales in the pre-main sequence, the main sequence (MS), and around the MS turnoff. Although a substantial amount of angular momentum remains in the interior, rotation is only a minor perturbation on the structure and ages of globular cluster stars. Even models with large initial angular momenta have MS lifetimes that are within 1 percent of those of standard models of the same mass and composition. Therefore, rotation does not affect age estimates of globular clusters from isochrone fitting. Furthermore, the models suggest that because rotation is not likely to affect horizontal-branch (HB) morphology, it does not affect significantly age estimates from the Delta-V method. Nevertheless, the internal angular momentum in the models is consistent with observations of surface rotational velocities on the HB, which require the preservation of a large reservoir of internal angular momentum.

Deliyannis, Constantine P.↗
DOE OSTI2021

Comments on the SURFplus reactive burn model

The SURFplus reactive burn model is intended for heterogeneous solid HE that produce an excess amount of carbon. It utilizes a fast hotspot reaction (SURF model) plus a second slow reaction for the energy release from carbon clustering. The fast reaction dominates shock initiation, though the fast rate parameters are slightly affected by the late energy release from the slow reaction. The slow reaction has a significant affect on propagating detonation waves. Propagating detonation waves are characterized by the curvature effect; i.e., detonation speed $D_n$ as function of the local front curvature κ. The $D_n(κ)$ curves have a qualitative different shape. This results from the sensitivity of the slope of the $D_n(κ)$ curve to the reaction-zone width up to the sonic point, and the sonic point moving as κ increases from the end of the slow reaction to the neighborhood of the end of the fast reaction. For PBX 9502, the steep slope for small curvature is determined by the slow reaction, while the lower slope for larger curvature is determined by the fast reaction rate in the high detonation pressure regime. The remainder of this paper is organized as follows. In section 2 we review the assumptions of the Shaw and Johnson carbon cluster model used by the SURFplus model for the slow reaction. Section 3 describes in detail the mixture model for a partly burned HE. The form of the slow rate used by the SURFplus model is described in section 4. We conclude with a brief discussion of applying a burn model with 2 rates to either a metalized or a composite PBX.

42 ENGINEERING↗
DOE OSTI2023

The Evolution of Population III and Extremely Metal-poor Binary Stars

Numerical simulations have now shown that Population III (Pop III) stars can form in binaries and small clusters and that these stars can be in close proximity to each other. If so, they could be subject to binary interactions such as mass exchange that could profoundly alter their evolution, ionizing UV and Lyman–Werner photon emission and explosion yields, with important consequences for early cosmological reionization and chemical enrichment. Here we investigate the evolution of Pop III and extremely metal-poor binary stars with the MESA code. We find that interactions ranging from stable mass transfer to common envelope evolution can occur in these binaries for a wide range of mass ratios and initial separations. Mass transfer can nearly double UV photon yields in some of these binaries with respect to their individual stars by extending the life of the companion star, which in turn can enhance early cosmological reionization but also suppress the formation of later generations of primordial stars. Binary interactions can also have large effects on the nucleosynthetic yields of the stars by promoting or removing them into or out of mass ranges for specific SN types. We provide fits to total photon yields for the binaries in our study for use in cosmological simulations.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

How Well Can Quantum Embedding Method Predict the Reaction Profiles for Hydrogenation of Small Li Clusters?

Quantum computing leverages the principles of quantum mechanics in novel ways to tackle complex chemistry problems that cannot be accurately addressed using traditional quantum chemistry methods. However, the high computational cost and available number of physical qubits with high fidelity limit its application to small chemical systems. This work employed a quantum-classical framework which features a quantum active space-embedding approach to perform simulations of chemical reactions that require up to 14 qubits. This framework was applied to prototypical example metal hydrogenation reactions: the coupling between hydrogen and Li 2 , Li 3 , and Li 4 clusters. Particular attention was paid to the computation of barriers and reaction energies. The predicted reaction profiles compare well with advanced classical quantum chemistry methods, demonstrating the potential of the quantum embedding algorithm to map out reaction profiles of realistic gas-phase chemical reactions to ascertain qualitative energetic trends. Additionally, the predicted potential energy curves provide a benchmark to compare against both current and future quantum embedding approaches.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Precision Loading and Delivery of Molecular Cargo by Size-Controlled Coacervation of Gold Nanoparticles Functionalized with Elastin-like Peptides

Thermoresponsive elastin-like peptides (ELPs) have been extensively investigated in biotechnology and medicine, but little attention has been paid to the process by which coacervation causes ELP-decorated particles to aggregate. Here, using gold nanoparticles (AuNPs) functionalized with a cysteine-terminated 96-repeat of the VPGVG sequence (V96-Cys), we show that the size of the clusters that reversibly form above the ELP transition temperature can be finely controlled in the 250 to 930 nm range by specifying the concentration of free V96-Cys in solution and using AuNPs of different sizes. We further find that the localized surface plasmon resonance peak of the embedded AuNPs progressively red-shifts with cluster size, likely due to an increase in particle–particle contacts. We exploit this fine control over size to homogeneously load precise amounts of the dye Nile Red and the antibiotic Tetracycline into clusters of different hydrodynamic diameters and deliver cargos near-quantitatively by deconstructing the aggregates below the ELP transition temperature. Beyond establishing a key role for free ELPs in the agglomeration of ELP-functionalized particles, our results provide a path for the thermally controlled delivery of precise quantities of molecular cargo. This capability might prove useful in combination photothermal therapies and theranostic applications, and to trigger spatially and temporally uniform responses from biological, electronic, or optical systems.

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

Kinetic Model of Acid Gas Induced Defect Propagation in Zeolitic Imidazolate Frameworks

Understanding the degradation of nanoporous materials under exposure to common acid gas contaminants (e.g., SO 2 , CO 2 , NO 2 , and H 2 S) is essential to elongate their lifetime and thus enable their practical applications in separations and catalysis. Previous theoretical investigations have focused on the formation of isolated point defects, which are insufficient to provide direct insights into the long-term evolution of the bulk properties of materials such as zeolitic imidazolate frameworks (ZIFs) under sustained acid gas exposure. Here, to bridge this divide in both length and time scales, we developed a first-principles lattice-based kinetic model to simulate the defect propagation and bulk material breakdown in ZIFs. This model closely reproduces the experimentally measured macroscopic evolution of the time-dependent bulk materials proprieties and also yields important new insights regarding the autocatalytic nature of ZIF degradation and the spatial distribution of defects. Our results suggest new experimental directions to identify nascent defect clusters in degraded ZIFs and avenues to mitigate degradation under challenging conditions of acid gas exposure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

MBX: A many-body energy and force calculator for data-driven many-body simulations

Many-Body eXpansion (MBX) is a C++ library that implements many-body potential energy functions (PEFs) within the “many-body energy” (MB-nrg) formalism. MB-nrg PEFs integrate an underlying polarizable model with explicit machine-learned representations of many-body interactions to achieve chemical accuracy from the gas to the condensed phases. MBX can be employed either as a stand-alone package or as an energy/force engine that can be integrated with generic software for molecular dynamics and Monte Carlo simulations. MBX is parallelized internally using Open Multi-Processing and can utilize Message Passing Interface when available in interfaced molecular simulation software. In this study, MBX enables classical and quantum molecular simulations with MB-nrg PEFs, as well as hybrid simulations that combine conventional force fields and MB-nrg PEFs, for diverse systems ranging from small gas-phase clusters to aqueous solutions and molecular fluids to biomolecular systems and metal-organic frameworks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Deep Generative Models that Solve PDEs: Distributed Computing for Training Large Data-Free Models

Recent progress in scientific machine learning (SciML) has opened up the possibility of training novel neural network architectures that solve complex partial differential equations (PDEs). Several (nearly data free) approaches have been recently reported that successfully solve PDEs, with examples including deep feed forward networks, generative networks, and deep encoder-decoder networks. However, practical adoption of these approaches is limited by the difficulty in training these models, especially to make predictions at large output resolutions (≥1024×1024). Here we report on a software framework for data parallel distributed deep learning that resolves the twin challenges of training these large SciML models - training in reasonable time as well as distributing the storage requirements. Our framework provides several out of the box functionality including (a) loss integrity independent of number of processes, (b) synchronized batch normalization, and (c) distributed higher-order optimization methods. We show excellent scalability of this framework on both cloud as well as HPC clusters, and report on the interplay between bandwidth, network topology and bare metal vs cloud. We deploy this approach to train generative models of sizes hitherto not possible, showing that neural PDE solvers can be viably trained for practical applications. We also demonstrate that distributed higher-order optimization methods are 2-3× faster than stochastic gradient-based methods and provide minimal convergence drift with higher batch-size.

PDEs↗
DOE OSTI2021

Real Space Quantum Cluster Formulation for the Typical Medium Theory of Anderson Localization

We develop a real space cluster extension of the typical medium theory (cluster-TMT) to study Anderson localization. By construction, the cluster-TMT approach is formally equivalent to the real space cluster extension of the dynamical mean field theory. Applying the developed method to the 3D Anderson model with a box disorder distribution, we demonstrate that cluster-TMT successfully captures the localization phenomena in all disorder regimes. As a function of the cluster size, our method obtains the correct critical disorder strength for the Anderson localization in 3D, and systematically recovers the re-entrance behavior of the mobility edge. From a general perspective, our developed methodology offers the potential to study Anderson localization at surfaces within quantum embedding theory. This opens the door to studying the interplay between topology and Anderson localization from first principles.

36 MATERIALS SCIENCE↗
NASA NTRS1978

Photometric studies of composite stellar systems. I - CO and JHK observations of E and S0 galaxies

Multiaperture infrared photometric observations of the central regions of 51 early-type galaxies and of the integrated light of five globular clusters are presented. These data are compared with selected optical observations and with various model predictions. The main results of the work are: (1) the observed parameters for the brighter galaxies, particularly the CO index and the V-K color, agree with the predictions of stellar synthesis models characterized by giant-dominated populations with mass/visual luminosity ratios less than 10; (2) the galaxian broad-band colors tend to redden with increasing luminosity and decreasing aperture size; (3) for the globular clusters, there is evidence that the integrated colors become redder with increasing metallicity; and (4) in bright galaxies the relative changes of U-V, V-J, and J-K as functions of radius may differ from the relative changes as functions of luminosity at a fixed radius.

Frogel, J. A.↗
DOE OSTI2022

How a Formate Dehydrogenase Responds to Oxygen: Unexpected O 2 Insensitivity of an Enzyme Harboring Tungstopterin, Selenocysteine, and [4Fe–4S] Clusters

The reversible two-electron interconversion of formate and CO 2 is catalyzed by both nonmetallo- and metallo-formate dehydrogenases (FDHs). The latter group comprises molybdenum- or tungsten-containing enzymes with the metal coordinated by two equivalents of a pyranopterin cofactor, a cysteinyl or selenocysteinyl (Sec) ligand supplied by the polypeptide, and a catalytically essential terminal sulfido ligand. In addition, these biocatalysts incorporate one or more [4Fe–4S] clusters for facilitating long-distance electron transfer. However, an interesting dichotomy arises when attempting to understand how the metallo-FDHs react with O 2 . Whereas existing scholarship portrays these enzymes as being unable to perform in air due to extreme O 2 lability of their metal centers, studies dating as far back as the 1930s emphasize that some of these systems exhibit formate oxidase (FOX) activity, coupling formate oxidation to O 2 reduction. Therefore, to reconcile these conflicting views, we explored context-dependent functional linkages between metallo-FDHs and their cognate electron acceptors within the same organism vis-à-vis catalysis under atmospheric O 2 . Here, we report the discovery and characterization of an O 2 -insensitive FDH2 from the sulfate-reducing bacterium Desulfovibrio vulgaris Hildenborough (DvH) that ligates tungsten, Sec, and four [4Fe–4S] clusters. By advancing a robust expression platform for its recombinant production, we eliminate both the requirement of nitrate or azide during purification and reductive activation with thiols and/or formate prior to catalysis. Because the distinctive spectral signatures of formate-reduced DvH-FDH2 remain invariant under anaerobic and aerobic conditions, we benchmarked the enzyme activity in air, identifying CO 2 as the catalytic product. Full reaction progress curve analysis discloses a high catalytic efficiency when probed with a high-potential artificial electron acceptor. Furthermore, we show that DvH-FDH2 enables near-stoichiometric hydrogen peroxide production without superoxide release to achieve O 2 insensitivity. Notably, simultaneous electron transfer to cytochrome c and O 2 reveals that metal-based electron bifurcation is operational in this system. Taken together, our work proves the co-occurrence of redox bifurcated FDH and FOX activities within a metalloenzyme scaffold. These findings set the stage for uncovering previously unknown O 2 -insensitive flavin-based electron bifurcation mechanisms, as well as for developing authentic formate/air biofuel cells, engineering O 2 -stable FDHs and biohybrid metallocatalysts, and discerning formate bioenergetics of gut microbiota.

13C NMR↗
DOE OSTI2022

Unveiling the mechanism of the photocatalytic reduction of CO 2 to formate promoted by porphyrinic Zr-based metal–organic frameworks

A complete picture of the reaction mechanism responsible for the photocatalytic reduction of CO 2 into formate promoted by the Zr-based porphyrinic MOF-545 (PCN-222) in acetonitrile/triethanolamine (CH 3 CN/TEOA) solutions is provided for the first time by combining experimental and computational approaches. Firstly, we combined the metalation of the porphyrin linkers and the synthesis under microwave conditions of nano-sized materials (150–200 nm) to reach one of the highest CO 2 RR activities under visible light irradiation reported so far for a MOF-based catalyst in terms of formate production (identified in all cases as the sole product), i.e., 6000 μmol g –1 after 4 h for the NanoMOF-545(Fe). A thorough mechanistic study of CO 2 RR is provided afterwards, which elucidated the respective roles of TEOA, porphyrin linkers and Zr 6 -nodes. Photophysical measurements of both metalated and unmetalated MOFs excluded the prevailing belief of ligand-to-Zr 6 cluster charge-transfer state formation, while bulk photolysis proved that the porphyrinic linkers of the MOF promote the photooxidation of TEOA under catalytic conditions. DFT calculations allowed characterization with atomistic detail of a novel reaction mechanism whereby TEOA˙ radicals generated photochemically at the porphyrinic linkers play the crucial role of transferring a formal hydride to a CO 2 molecule activated on a Zr IV center, which acts as a Lewis acid. Notably, this mechanism backed by additional experimental assays explains the experimental activity trends observed upon metalation, on the basis of the ability of the materials to accomplish the photo-oxidation of TEOA. Here, while elucidating the reaction pathways at work in Zr 6 -based MOFs with chromophore linkers, the findings reported herein pinpoint new mechanistic features capable of rationalizing other light-driven reactions making use of TEOA (or structurally related donors) and ultimately, inspire the bottom-up design of new catalysts and catalytic routes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2023

Far-Infrared Line Emission from the Outer Galaxy Cluster Gy 3–7 With SOFIA/FIFI-LS: Physical Conditions and UV Fields

Context. Far-infrared (FIR) line emission provides key information about the gas cooling and heating due to shocks and UV radiation associated with the early stages of star formation. Gas cooling via FIR lines might, however, depend on metallicity. Aims. We aim to quantify the FIR line emission and determine the spatial distribution of the CO rotational temperature, ultraviolet (UV) radiation field, and H2 number density toward the embedded cluster Gy 3–7 in the CMa–l224 star-forming region, whose metallicity is expected to be intermediate between that of the Large Magellanic Cloud and the Solar neighborhood. By comparing the total luminosities of CO and [O I] toward Gy 3–7 with values found for low- and high-mass protostars extending over a broad range of metallicities, we also aim to identify the possible effects of metallicity on the FIR line cooling within our Galaxy. Methods. We studied SOFIA/FIFI-LS spectra of Gy 3–7, covering several CO transitions from J = 14–13 to 31-30, the OH doublet at 79 µm, the [O I] 63.2 and 145.5 µm, and the [C II] 158 µm lines. The field of view covers a 2 0 × 1 0 region with a resolution of ∼7 00–1800 . Results. The spatial extent of CO high-J (Jup ≥14) emission resembles that of the elongated 160 µm continuum emission detected with Herschel, but its peaks are offset from the positions of the dense cores. The [O I] lines at 63.2 µm and 145.5 µm follow a similar pattern, but their peaks are found closer to the positions of the cores. The CO transitions from J = 14–13 to J = 16–15 are detected throughout the cluster and show a median rotational temperature of 170 ± 30 K on Boltzmann diagrams. Comparisons to other protostars observed with Herschel show a good agreement with intermediate-mass sources in the inner Galaxy. Assuming an origin of the [O I] and high-J CO emission in UV-irradiated C−shocks, we obtained pre-shock H2 number densities of 104–105 cm−3 and UV radiation field strengths of 0.1–10 Habing fields (G0). Conclusions. Far-IR line observations reveal ongoing star formation in Gy 3–7, dominated by intermediate-mass Class 0/I young stellar objects. The ratio of molecular-to-atomic far-IR line emission shows a decreasing trend with bolometric luminosities of the protostars. However, it does not indicate that the low-metallicity has an impact on the line cooling in Gy 3–7.

stars: formation↗