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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Fundamental Interactions of Bimetallic Cu x Pd y ( x + y = 4) Clusters Supported on the α-WC(0001) Surface and Their Performance for CO 2 Adsorption and Dissociation

The tungsten carbide α-WC(0001) surface, an active system for the activation of H 2 and important hydrogenation processes involving unsaturated hydrocarbons, can serve as a support of bimetallic clusters to produce materials with unique catalytic properties, opening routes for a wide range of technical applications. In particular, Cu x Pd y clusters are of particular interest because they combine metals with different properties. A stochastic method was applied to obtain the geometry of Cu x Pd y (x + y = 4) bare clusters, evaluating thousands of possibilities to obtain stable structures, yielding one isomer for Cu 4 , Cu 2 Pd 2 , Cu 1 Pd 3 , and Pd 4 and two isomers for Cu 3 Pd 1 . These clusters were supported on C and W terminations of the tungsten carbide (0001) surface, exploring all of the binding possibilities. The adsorption energies on the C and W terminations are in the ranges from −2.51 to −3.02 eV and from −2.26 to −3.30 eV, respectively. The strongest and weakest binding was seen for monometallic Cu 4 and Pd 4 clusters on both C and W terminations, while the Cu-Pd bimetallics have intermediate adsorption energies but lack a clear trend in terms of composition. The location of Cu x Pd y clusters over the (0001) surface induces a decrease in the work function relative to the pristine surface, while the cluster-surface Bader charge transfer and variations in the partial density of states point to changes in the electronic structure of the carbide atoms upon binding of the metallic clusters. The d-band center of the Cu x Pd y deposited on WC(0001) indicates an intermediate reactivity among Cu(111) and Pd(111) surfaces, modulating the reactivity with small numbers of Cu and Pd atoms, i.e., atom economy in catalyst design. The likelihood of existence of the most stable Cu x Pd y (x + y = 4) clusters in the temperature range of 298-400 K is 100%. The composite Cu x Pd y /α-WC(0001) (x + y = 4), is a nontrivial system since 22 isomers are needed to completely describe its structural properties. Among the isomers, seven structures are necessary to represent Cu 3 Pd 1 /α-WC(0001), five for Pd 4 /α-WC(0001), two for Cu 4 /α-WC(0001), and four for Cu 2 Pd 2 /α-WC(0001) and Cu 1 Pd 3 /α-WC(0001). The large number of cluster isomers supported on the tungsten carbide surface opens the door for several applications in the heterogeneous catalysis of the Cu x Pd y /α-WC(0001) composite, with the possibility of modulating the geometric, electronic, and chemical properties according to a desired application. Test studies for the adsorption of CO 2 indicate that the Cu x Pd y /α-WC(0001) composites are highly active for the adsorption and decomposition of the molecule, with bimetallic and admetal-carbide interactions playing a key role in the binding performance. In conclusion, this high activity indicates that these systems should be useful as catalysts for the conversion of CO 2 to oxygenates or light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

When clusters are superclusters

Recent research on substructure in clusters and superclusters of galaxies is critically surveyed, with an emphasis on the distinction (based on physical size and dynamic state) between the two classes of structures. The cosmological and large-scale structural implications of substructure in rich clusters are analyzed, using N-body-simulation results, and illustrated for the clusters A98 and A548. Consideration is also given to gravitational lensing of distant quasars by intervening clusters and the interpretation of the matter distribution on scales larger than about 5 Mpc. It is determined that A98 and A548 are superclusters.

Geller, M. J.↗
DOE OSTI2021

Localized High Concentration Electrolyte and Its Effects on Polysulfide Structure in Solution

Lithium–sulfur batteries (LiSB) are a promising next-generation lithium energy storage technology that offers a multifold improvement over the traditional lithium-ion battery. However, the LiSB still faces the unresolved issue of the polysulfide shuttle effect. This phenomenon arises from the dissolution of sulfur intermediate reduction products into the electrolyte, which then causes a cascade of issues throughout the battery. Many mitigation strategies have been proposed to counteract this effect including the use of novel electrolyte compositions. Recently, there has been increased focus on the use of hydrofluorinated ethers as a major constituent of an electrolyte for lithium batteries. Previous studies have reported that the presence of these species create localized high concentration electrolytes (LHCE) which can have many advantages resulting in improved battery performance. Here, we report on how the inclusion of a hydrofluorinated ether BTFE (bis(2,2,2-trifluoroethyl) ether) modifies the general properties of a LiSB electrolyte and the structure of dissolved polysulfide species in the electrolyte. Here, we found that the inclusion of BTFE does not modify the primary solvation structure of Li + directly but actively participates in secondary solvation shells. With a high concentration of BTFE, the LHCE formation is observed by the presence of clusters of non-BTFE molecules. The structure of polysulfide species in solution was modified by the BTFE in the same way. Much of the primary solvation structure was kept, but the presence of BTFE increased polysulfide–polysulfide clustering. These results indicate that the polysulfide solubility will be limited due to the promotion of clustering.

25 ENERGY STORAGE↗
DOE OSTI2021

Observation of spontaneous x-ray magnetic circular dichroism in a chiral antiferromagnet

X-ray magnetic circular dichroism (XMCD) signals are usually absent in antiferromagnets. In this paper, we report the observation of spontaneous XMCD spectra originating from the inverse triangular spin structure, or the polarization of the cluster magnetic octupole, in the chiral antiferromagnet Mn 3 Sn thin film. Finally, the result is consistent with the recent theoretical predictions that the inverse triangular spin structure can give rise to finite XMCD signals in the absence of net magnetization [J. Phys. Soc. Jpn 89, 083703 (2020) and Phys. Rev. Lett. 126, 157402 (2021)].

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1988

The evolution of the system of globular clusters

The physical processes affecting the evolution of the system of globular clusters are reviewed. Aspects of internal structure evolution discussed include evaporation, core collapse, expansion, tidal shocks, and interaction with other massive components of the Galaxy such as black holes, molecular clouds, and other clusters. The evolution of orbital parameters is examined, including dynamical friction, scattering by massive subcomponents, and interactions with nearby systems. In addition, an overview of the system evolution is presented.

Ostriker, Jeremiah P.↗
NASA NTRS2017

Exploring Connectivity in Sequence Space of Functional RNA

Emergence of replicable genetic molecules was one of the marking points in the origin of life, evolution of which can be conceptualized as a walk through the space of all possible sequences. A theoretical concept of fitness landscape helps to understand evolutionary processes through assigning a value of fitness to each genotype. Then, evolution of a phenotype is viewed as a series of consecutive, single-point mutations. Natural selection biases evolution toward peaks of high fitness and away from valleys of low fitness. whereas neutral drift occurs in the sequence space without direction as mutations are introduced at random. Large networks of neutral or near-neutral mutations on a fitness landscape, especially for sufficiently long genomes, are possible or even inevitable. Their detection in experiments, however, has been elusive. Although a few near-neutral evolutionary pathways have been found, recent experimental evidence indicates landscapes consist of largely isolated islands. The generality of these results, however, is not clear, as the genome length or the fraction of functional molecules in the genotypic space might have been insufficient for the emergence of large, neutral networks. Thorough investigation on the structure of the fitness landscape is essential to understand the mechanisms of evolution of early genomes. RNA molecules are commonly assumed to play the pivotal role in the origin of genetic systems. They are widely believed to be early, if not the earliest, genetic and catalytic molecules, with abundant biochemical activities as aptamers and ribozymes, i.e. RNA molecules capable, respectively, to bind small molecules or catalyze chemical reactions. Here, we present results of our recent studies on the structure of the sequence space of RNA ligase ribozymes selected through in vitro evolution. Several hundred thousands of sequences active to a different degree were obtained by way of deep sequencing. Analysis of these sequences revealed several large clusters defined such that every sequence in a cluster can be reached from any other sequence in the same cluster through a series of single point mutations. Sequences in a single cluster appear to adopt more than one secondary structure. The mechanism of refolding within a single cluster was examined. To shed light on possible evolutionary paths in the space of ribozymes, the connectivity between clusters was investigated. The effect of length of RNA molecules on the structure of the fitness landscape and possible evolutionary paths was examined by way of comparing functional sequences of 20 and 80 nucleobases in length. It was found that sequences of different lengths shared secondary structure motifs that were presumed responsible for catalytic activity, with increasing complexity and global structural rearrangements emerging in longer molecules.

Wei, Chenyu↗
DOE OSTI2025

Influence of counterion substitution on the properties of imidazolium-based ionic liquid clusters

Due to their unique physiochemical properties that may be tailored for specific purposes, ionic liquids (ILs) have been investigated for various applications, including chemical separations, catalysis, energy storage, and space propulsion. The different cations and anions comprising ILs may be selected to optimize a range of desired properties, such as thermal stability, ionic conductivity, and volatility, leading to the designation of certain ILs as designer “green” solvents. The effect of counterions on the properties of ILs is of both fundamental scientific interest and technological importance. Herein, we report a systematic experimental and theoretical investigation of the size, charge, stability toward dissociation, and geometric/electronic structure of 1-ethyl-3-methyl imidazolium (EMIM)-based IL clusters containing two different atomic counterions (i.e., bromide [Br − ] and iodide [I − ]). This work extends our studies of EMIM + cations with atomic chloride (Cl − ) and molecular tetrafluoroborate (BF 4 − ) anions reported previously by Baxter et al. [Chem. Mater. 34, 2612 (2022)] and Zhang et al . [J. Phys. Chem. Lett. 11, 6844 (2020)], respectively. Distributions of anionic IL clusters were generated in the gas phase using electrospray ionization and characterized by high mass resolution mass spectrometry, energy-resolved collision-induced dissociation, and negative ion photoelectron spectroscopy experiments. The experimental results reveal anion-dependent trends in the size distribution, relative abundance, ionic charge state, stability toward dissociation, and electron binding energies of the IL clusters. Complementary global optimization theory provides molecular-level insights into the bonding and electronic structure of a selected subset of clusters, including their low energy structures and electrostatic potential maps, and how these fundamental characteristics are influenced by anion substitution. Collectively, our findings demonstrate how the fundamental properties of ILs, which determine their suitability for many applications, may be tuned by substituting counterions. These observations are critical in the sub-nanometer cluster size regime where phenomena do not scale predictably to the bulk phase, and each atom counts toward determining behavior.

cluster↗
DOE OSTI2020

Structure and Function of BorB, the Type II Thioesterase from the Borrelidin Biosynthetic Gene Cluster

α/β hydrolases make up a large and diverse protein superfamily. In natural product biosynthesis, cis-acting thioesterase α/β hydrolases can terminate biosynthetic assembly lines and release products by hydrolyzing or cyclizing the biosynthetic intermediate. Thioesterases can also act in trans, removing aberrant intermediates and restarting stalled biosynthesis. Knockout of this "editing" function leads to reduced product titers. The borrelidin biosynthetic gene cluster from Streptomyces parvulus Tü4055 contains a hitherto uncharacterized stand-alone thioesterase, borB. In this work, we demonstrate that purified BorB cleaves acyl substrates with a preference for propionate, which supports the hypothesis that it is also an editing thioesterase. The crystal structure of BorB shows a wedgelike hydrophobic substrate binding crevice that limits substrate length. To investigate the structure-function relationship, we made chimeric BorB variants using loop regions from characterized homologues with different specificities. BorB chimeras slightly reduced activity, arguing that the modified region is a not major determinant of substrate preference. Overall, the structure-function relationships described here contribute to the process of elimination for understanding thioesterase specificity and, ultimately, engineering and applying trans-acting thioesterases in biosynthetic assembly lines.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Crystal structure and shape selection in the growth of 3D metallic crystallites on layered materials: Fe on MoS 2

Nucleation and growth of supported 3D metal clusters or crystallites during deposition on MoS 2 , or on other weakly-adhering layered materials, can potentially produce diverse growth shapes, and even crystal structures differing from the bulk metal. For Fe deposition on MoS 2 , SEM and AFM observations reveal three distinct crystallite shapes. By comparison with atomistic structure models incorporating realistic Fe-MoS 2 interface structures, here we conclude that these are: triangular fcc(111) pyramids with sloped {100} side facets; bcc(110) A-frame tents with sloped {100} side facets; and bcc(110) mesas with vertical {100} and {110} side facets. The following picture is proposed for the competitive formation of clusters and crystallites with different structures: (i) small nanoclusters formed at the onset of deposition exhibit facile fluxional dynamics allowing sampling of different crystal structures and shapes; (ii) sufficient fluxionality implies a Boltzmann distribution of sampled structures, and thus coexistence of different structures follows from the demonstrated similar energies for those structures; (iii) growing clusters reach a threshold size above which the characteristic time scale for restructuring exceeds that for cluster growth. Thereafter, clusters are locked-in to a specific crystal structure and shape as revealed by imaging of larger crystallites. Despite a penalty for fcc(111) over bcc(111) pyramids based on bulk energetics, favorable surface and interface energies makes them preferable for smaller sizes.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

MEDPRAT Treatment Clusters: Improving Representation of Mission Medical Risk

INTRODUCTION The Medical Extensible Dynamic Probabilistic Risk Assessment Tool (MEDPRAT) implements a computational model that aims to quantify spaceflight medical risk by utilizing probabilistic techniques to simulate critical event incidence and outcomes over thousands of simulated mission trials. The goal of MEDPRAT is to characterize mission medical risk and provide insight into medical resource utilization. In order to analyze the medical resource space, treatment must be mapped from each simulated condition, and resources consumed as a result of this treatment must be tracked throughout the course of the mission. A new MEDPRAT feature, ‘treatment clusters’, provide a more sophisticated method of defining the structure and interaction between resources, more closely mimicking the way treatment is carried out clinically. METHODS Treatment clusters expand on the two existing treatment groupings (combination and alternate) adding a new grouping: bundled treatment. Treatment clusters may be combined to any depth, giving users the ability to specify complex treatment trees whose behavior is governed by several user-specified parameters. This approach emphasizes reusability, as treatment clusters, once defined, can be used to create more complex treatment trees or applied to many conditions. By configuring parameters for contribution, efficacy, necessity, primacy, and equivalence, resource relationships and dependencies can be more accurately represented, thereby allowing users to build capabilities with desired treatment properties, for example an intravenous capability for conditions such as anaphylaxis, acute radiation syndrome, etc. MEDPRAT v1.0 remains backward compatible with existing treatment structures, giving users the ability to define new treatment clusters as evidence becomes available, without having to recode their existing treatment databases. In addition to facilitating the representation of more complex treatment options, by pairing treatment clusters with the internal optimization routine, the MEDPRAT set selector, medical resources can be identified as organized in bundles, where appropriate, so that optimized resource sets include groups of highly-dependent resources only when all resources of the group are together. For example, it would be wasteful to include ultrasound gel but not an ultrasound machine, since the gel provides no benefit as a treatment without the ultrasound machine. With treatment clusters, the user may require that both resources are available to provide any benefit as treatment, so that if one resource is optimized out of the set, the other resource will be optimized out as well. RESULTS AND CONCLUSIONS We will report on MEDPRAT treatment clusters used in a bundling study under the IMPACT project of the ExMC element. We will discuss an example of a complex treatment tree. Through the implementation of this feature MEDPRAT enables treatment to be defined and applied in a way that is more representative of the real world, providing more accurate insight into mission medical risk and the medical resource space.

Lawrence Leinweber↗
NASA NTRS2008

Multiscale Computer Simulation of Failure in Aerogels

Aerogels have been of interest to the aerospace community primarily for their thermal properties, notably their low thermal conductivities. While such gels are typically fragile, recent advances in the application of conformal polymer layers to these gels has made them potentially useful as lightweight structural materials as well. We have previously performed computer simulations of aerogel thermal conductivity and tensile and compressive failure, with results that are in qualitative, and sometimes quantitative, agreement with experiment. However, recent experiments in our laboratory suggest that gels having similar densities may exhibit substantially different properties. In this work, we extend our original diffusion limited cluster aggregation (DLCA) model for gel structure to incorporate additional variation in DLCA simulation parameters, with the aim of producing DLCA clusters of similar densities that nevertheless have different fractal dimension and secondary particle coordination. We perform particle statics simulations of gel strain on these clusters, and consider the effects of differing DLCA simulation conditions, and the resultant differences in fractal dimension and coordination, on gel strain properties.

Good, Brian S.↗
DOE OSTI2024

Unique Aluminum Clusters Stabilized by Cation‐Ligand Cooperativity

Abstract Two novel cyclic Al 3 clusters, Li 2 [Al 3 (PR 2 ) 6 ] ⋅ 2(Et 2 O) [R=Ph ( 1 ), Cy ( 2 )] were synthesized through salt metathesis of metastable AlCl ⋅ (Et 2 O) n solutions with LiPR 2 . Both complexes were characterized by single crystal X‐Ray diffraction and their solid state and electronic structures are compared to previously reported cyclic Al 3 clusters. Compounds 1 and 2 were further characterized using density functional theory (DFT) methods to understand the nature of the free electron and the three‐center two‐electron Al−Al bonds. Calculations revealed that both clusters are influenced by pseudo Jahn‐Teller distortion and are likely in equilibrium between two low energy bonding states. The solid‐state structures of 1 and 2 are unique among Al 3 clusters, while the electronic structure is similar to the previously reported [Si t 4 Al 3 ]. In aluminum chemistry, 1 and 2 are rare examples of clusters containing isoelectronic cores in different ligand environments. The effects of the phosphide ligand sphere and strongly coordinated lithium atoms are discussed in detail.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Manipulating the Assembly and Architecture of Fibrillar Silk

Silk is a unique and exceptionally strong biological material. However, no synthetic method has yet come close to replicating the properties of natural silk. This shortfall is attributed to an insufficient understanding of both silk nanofibril structure and the mechanism of formation. Here in situ atomic force microscopy (AFM) and photo-induced force microscopy (PiFM) is utilized to investigate the formation process and define the basic structural paradigm of individual silk nanofibrils. By visualizing the multistage process of silk nanofibril formation, the importance of conformational transformations along the assembly pathway is revealed. Unfolded silk structures initially accumulate into amorphous clusters, which then evolve into crystal nuclei via conformational transformation into β-crystallites. Nanofibril elongation then occurs through the attachment of silk molecules at a single end of the nanofibril tip; this is facilitated through the formation of a new amorphous cluster that then repeats the aforementioned conformational transformation. However, enzymatic digestion of the amorphous regions leads to direct, rapid elongation of β-crystalline fibers. These findings imply that the energy landscape is characterized by shallow minima associated with intermediate states, which can be eliminated by introducing β-crystallites, and motivate research into the directed modification of the silk assembly pathway to select for features beneficial to specific applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Production of light (anti)nuclei in pp collisions at $ \sqrt{s} $=13 TeV

Understanding the production mechanism of light (anti)nuclei is one of the key challenges of nuclear physics and has important consequences for astrophysics, since it provides an input for indirect dark-matter searches in space. In this paper, the latest results about the production of light (anti)nuclei in pp collisions at $\sqrt{s}$ = 13 TeV are presented, focusing on the comparison with the predictions of coalescence and thermal models. For the first time, the coalescence parameters B 2 for deuterons and B 3 for helions are compared with parameter-free theoretical predictions that are directly constrained by the femtoscopic measurement of the source radius in the same event class. A fair description of the data with a Gaussian wave function is observed for both deuteron and helion, supporting the coalescence mechanism for the production of light (anti)nuclei in pp collisions. This method paves the way for future investigations of the internal structure of more complex nuclear clusters, including the hypertriton.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Nonflammable Lithium Metal Full Cells with Ultra-high Energy Density Based on Coordinated Carbonate Electrolytes

Coupling thin Li metal anodes with high-capacity/high-voltage cathodes such as LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is a promising way to increase lithium battery energy density. Yet, the realization of high-performance full cells remains a formidable challenge. Here, we demonstrate a new class of highly coordinated, nonflammable carbonate electrolytes based on lithium bis(fluorosulfonyl)imide (LiFSI) in propylene carbonate/fluoroethylene carbonate mixtures. Utilizing an optimal salt concentration (4 M LiFSI) of the electrolyte results in a unique coordination structure of Li + -FSI - -solvent cluster, which is critical for enabling the formation of stable interfaces on both the thin Li metal anode and high-voltage NCM811 cathode. Under highly demanding cell configuration and operating conditions (Li metal anode = 35 μm, areal capacity/charge voltage of NCM811 cathode = 4.8 mAh cm -2 /4.6 V, and anode excess capacity [relative to the cathode] = 0.83), the Li metal-based full cell provides exceptional electrochemical performance (energy densities = 679 Wh kg cell -1 /1,024 Wh L cell -1 ) coupled with nonflammability.

25 ENERGY STORAGE↗
DOE OSTI2021

Solution and Interface Structure and Dynamics in Geochemistry: Gateway to Link Elementary Processes to Mineral Nucleation and Growth

Our understanding of the process of mineral nucleation is starting to evolve from the solely thermodynamical aspects in classical nucleation theory toward a mechanistic study of reactions influenced by solvation structures of ions and their dynamics. A knowledge of how these atomic and molecular interactions respond to changing solution composition and/or the nature of an interface will form a fundamental foundation to understand rate-limiting reactions and processes for nucleation and growth. Here, we review recent advances from multidisciplinary experimental and computational approaches of the structure and dynamics of aqueous solutions and mineral–liquid interfaces that will influence rates of nucleation (and growth behavior) both homogeneously in aqueous solutions and heterogeneously at mineral–liquid interfaces. Furthermore, these processes include structure (and extent) of solute clustering, solvent degrees of freedom, and the presence of noninnocent charge-balancing ions, all of which can drive the selectivity and exert control over nucleation mechanisms. Similar controlling reactions can also occur at interfaces with the added complexities of how solute ions interact with and assemble on surface sites and use different mechanisms from bulk solutes, such as lateral solvent exchanges between distinct surface sites. To gain a predictive understanding of nucleation chemistry, we emphasize several key knowledge gaps that will need to be addressed in this field and highlight the importance of combining computations and experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗