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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides

Here, the electronic structure and local coordination of binary (Mo 6 T 8 ) and ternary Chevrel Phases (M x Mo 6 T 8 ) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L 3 -edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides M x Mo 6 T 8 (M = Cu, Ni, x = 1–2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo 6 clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.

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

Mixed Valence {Ni 2+ Ni 1+ } Clusters as Models of Acetyl Coenzyme A Synthase Intermediates

Acetyl coenzyme A synthase (ACS) catalyzes the formation and deconstruction of the key biological metabolite, acetyl coenzyme A (acetyl-CoA). The active site of ACS features a {NiNi} cluster bridged to a [Fe4S4] n+ cubane known as the A-cluster. The mechanism by which the A-cluster functions is debated, with few model complexes able to replicate the oxidation states, coordination features, or reactivity proposed in the catalytic cycle. In this work, we isolate the first bimetallic models of two hypothesized intermediates on the paramagnetic pathway of the ACS function. The heteroligated {Ni 2+ Ni 1+ } cluster, [K(12-crown-4) 2 ][1], effectively replicates the coordination number and oxidation state of the proposed “A red ” state of the A-cluster. Addition of carbon monoxide to [1] - allows for isolation of a dinuclear {Ni 2+ Ni 1+ (CO)} complex, [K(12-crown-2) n ][2] (n = 1–2), which bears similarity to the “A NiFeC ” enzyme intermediate. Structural and electronic properties of each cluster are elucidated by X-ray diffraction, nuclear magnetic resonance, cyclic voltammetry, and UV/vis and electron paramagnetic resonance spectroscopies, which are supplemented by density functional theory (DFT) calculations. Calculations indicate that the pseudo-T-shaped geometry of the three-coordinate nickel in [1] – is more stable than the Y-conformation by 22 kcal mol –1 , and that binding of CO to Ni 1+ is barrierless and exergonic by 6 kcal mol –1 . UV/vis absorption spectroscopy on [2] - in conjunction with time-dependent DFT calculations indicates that the square-planar nickel site is involved in electron transfer to the CO π*-orbital. Further, we demonstrate that [2] - promotes thioester synthesis in a reaction analogous to the production of acetyl coenzyme A by ACS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Theoretical investigations of the structures and binding energies of Be(n) and Mg(n) (n = 3-5) clusters

The equilibrium geometries and binding energies of Be and Mg trimers, tetramers and pentamers have been determined using single and double excitation coupled cluster (CCSD) and complete active space self-consistent-field (CASSCF) multireference configuration interaction (MRCI) wave functions in conjunction with extended atomic basis sets. The best estimates of the cluster binding energies are 24, 83, and 110 kcal/mol for Be3, Be4, and Be5; and 9, 31, and 41 kcal/mol for Mg3, Mg4, and Mg5, respectively. A comparison of the MRCI and CCSD results shows that even the best single-reference approach (limited to single and double excitations) is not capable of quantitative accuracy in determining the binding energies of Be and Mg clusters.

Lee, Timothy J.↗
NASA NTRS2020

Cluster Analysis of Thermal Icequakes Using the Seismometer to Investigate Ice and Ocean Structure (SIIOS): Implications for Ocean World Seismology

Ocean Worlds are of high interest to the planetary community due to the potential habitability of their subsurface oceans. Over the next few decades several missions will be sent to ocean worlds including the Europa Clipper, Dragonfly, and possibly a Europa lander. The Dragonfly and Europa lander missions will carry seismic payloads tasked with detecting and locating seismic sources. The Seismometer to Investigate Ice and Ocean Structure (SIIOS) is a NASA PSTAR funded project that investigates ocean world seismology using terrestrial analogs. The goals of the SIIOS experiment include quantitatively comparing flight-candidate seismometers to traditional instruments, comparing single-station approaches to a small-aperture array, and characterizing the local seismic environment of our field sites. Here we present an analysis of detected local events at our field sites at Gulkana Glacier in Alaska and in Northwest Greenland approximately 80 km North of Qaanaaq, Greenland. Both field sites passively recorded data for about two weeks. We deployed our experiment on Gulkana Glacier in September 2017 and in Greenland in June 2018. At Gulkana there was a nearby USGS weather station which recorded wind data. Temperature data was collected using the MERRA satellite. In Greenland we deployed our own weather station to collect temperature and wind data. Gulkana represents a noisier and more active environment. Temperatures fluctuated around 0°C, allowing for surface runoff to occur during the day. The glacier had several moulins, and during deployment we heard several rockfalls from nearby mountains. In addition to the local environment, Gulkana is located close to an active plate boundary (relative to Greenland). This meant that there were more regional events recorded over two weeks, than in Greenland. Greenland’s local environment was also quieter, and less active. Temperatures remained below freezing. The Greenland ice was much thicker than Gulkana (~850 m versus ~100 m) and our stations were above a subglacial lake. Both conditions can reduce event detections from basal motion. Lastly, we encased our Greenland array in an aluminum vault and buried it beneath the surface unlike our array in Gulkana where the instruments were at the surface and covered with plastic bins. The vault further insulated the array from thermal and atmospheric events.

Marusiak, A. G.↗
DOE OSTI2025

Structure and Synthesizability of Iron–Sulfur Metal–Organic Frameworks

Sulfur-based metal–organic frameworks (MOFs) and coordination polymers (CPs) are an emerging class of hybrid materials that have received growing attention due to their magnetic, conductive, and catalytic properties with potential applications in electrocatalysis and energy storage. In this work, we report a high-throughput virtual screening protocol to predict the synthesizability of candidate metal–sulfur MOFs/CPs by computing the thermodynamically stable structures resulting from a particular combination of metal cluster, linker, cation, and synthetic conditions. Free energies are computed by using all-atom classical mechanical thermodynamic integration. Low-free-energy structures are refined using ab initio density functional theory, and pair distribution functions and powder X-ray diffraction patterns are calculated to complement and guide experimental structure determination. We validate the computational approach by retrospective predictions of the stable structure produced by experimental syntheses, and a subsequent screen predicts Fe 4 S 4 -BDT–TPP as a new thermodynamically stable one-dimensional (1D) CP comprising a redox-active Fe 4 S 4 cluster, a 1,4-benzenedithiolate (BDT) linker, and a tetraphenylphosphonium (TPP) countercation. Furthermore, this material is experimentally synthesized, and the 1D chain structure of the crystal is confirmed using microcrystal electron diffraction. The computational screening pipeline is generically transferable to neutral and ionic MOFs/CPs comprising arbitrary metal clusters, linkers, cations, and synthetic conditions, and we make it freely available as an open source tool to guide and accelerate the discovery and engineering of novel porous materials.

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

Optimal and robust reconstruction of BAO, redshift-space distortions and the Alcock-Paczynski effect

The goal of this project is to optimally reconstruct cosmological information that has been lost from large-scale clustering of galaxies due to cosmic structure growth. The outcome of our research will be used to improve dark energy and other cosmological constraints from the ongoing extended Baryon Oscillation Spectroscopic Survey (eBOSS) and the upcoming Dark Energy Spectroscopic Instrument (DESI). The large-scale galaxy clustering data contain two important features: the Baryon Acoustic Oscillations (BAO) and the overall shape from small to large scales.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Core Mass Estimates in Strong Lensing Galaxy Clusters: A Comparison between Masses Obtained from Detailed Lens Models, Single-halo Lens Models, and Einstein Radii

The core mass of galaxy clusters is both an important anchor of the radial mass distribution profile and probe of structure formation. With thousands of strong lensing galaxy clusters being discovered by current and upcoming surveys, timely, efficient, and accurate core mass estimates are needed. Here, we assess the results of two efficient methods to estimate the core mass of strong lensing clusters: the mass enclosed by the Einstein radius (M(<θ E ) where θ E is approximated from arc positions; Remolina González et al. 2020), and single-halo lens model (M SHM ; Remolina González et al. 2021), against measurements from publicly available detailed lens models (M DLM ) of the same clusters. We use data from the Sloan Giant Arc Survey, the Reionization Lensing Cluster Survey, the Hubble Frontier Fields, and the Cluster Lensing and Supernova Survey with Hubble. We find a scatter of 18.2% (8.2%) with a bias of -7.1% (1.0%) between M corr (<θ arcs ) (M SHM ) and M DLM . Last, we compare the statistical uncertainties measured in this work to those from simulations. This work demonstrates the successful application of these methods to observational data. As the effort to efficiently model the mass distribution of strong lensing galaxy clusters continues, we need fast, reliable methods to advance the field.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1989

WHT observations of cataclysmic variables in globular clusters. I - V101 in M5 during quiescence and outburst

WHT spectroscopy and photometry are used to investigate the structure of the cataclysmic vaiable V101, in the globular cluster M5. An encouraging consistency is found between the properties derived from the color, magnitude, radial-velocity variations and outburst light curve. All these indicate that V101's orbital period lies above the period gap, is at the distance of M5, and is probably a dwarf nova.

Naylor, T.↗
DOE OSTI2023

Hydrogen Evolution on Electrode–Supported Ptn Clusters: Ensemble of Hydride States Governs the Size Dependent Reactivity

We report the size-dependent activity and stability of supported Pt1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters outperform polycrystalline Pt in activity, with sizedependent stability. To understand the size effects, we use DFT calculations to study the structural fluxionality under varying potentials. We show that the clusters can reshape under H coverage and populate an ensemble of states with diverse stoichiometry, structure, and thus reactivity. Both experiment and theory suggest that electrocatalytic species are hydridic states of the clusters (~2 H/Pt). An ensemble-based kinetic model reproduces the experimental activity trend and reveals the role of metastable states. Furthermore, the stability trend is rationalized by chemical bonding analysis. Our joint study demonstrates the potential- and adsorbate-coverage-dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.

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

Au147(SPh)30(PPh3)12: A Geometrically Closed, but Electronically Open Triple‐Shell Icosahedral Gold Cluster and its Geometrically Open Counterpart

The aesthetic platonic solids have been known since ancient times, and the structure of all five platonic solids is also found in chemical compounds. While gold sub-nanometer clusters and gold nanoparticles with an icosahedral structure have been known for a long time to exist, a multi-shell icosahedral gold cluster at the intermediate size between 13 and thousands of atoms has been elusive. Here we present the synthesis and crystallographic characterization of the first triple-shell icosahedral metal cluster, Au147(SPh)30(PPh3)12 1. The gold core in 1 is stabilized by phosphines and thiolates, but surprisingly no staple motifs are formed. A second cluster, Au146(SPh)30(PPh3)12 2, cocrystallizes and is identified as having a closed electronic shell but can be considered as a geometrically open pendant of 1. The unique clusters are characterized experimentally by EDX, UV/vis, DLS, and EPR and theoretically by quantum chemical calculations.

Strienz, Markus↗
DOE OSTI2022

Symmetry-specific orientational order parameters for complex structures

A comprehensive framework of characterizing complex self-assembled structures with a set of orientational order parameters is presented. It is especially relevant in the context of using anisotropic building blocks with various symmetries. Two classes of tensor order parameters are associated with polyhedral nematic and bond orientational order. For the latter, a variation of classical bond order parameters (BOPs) is introduced, which takes advantage of the symmetry of constituent particles and/or expected crystalline phases. These symmetrized BOPs can be averaged over an entire system or assigned locally to an individual bond. By combining that with the bond percolation procedure, one is able to identify coherent domains within a self-assembled structure. As a demonstration of the proposed framework, we apply it to a simulated hybrid system that combines isotropic and patchy particles with octahedral symmetry. In conclusion, not only does the methodology allow one to identify individual crystalline domains but also it detects coherent clusters of a peculiar compact amorphous structure that is not space-filling and lacks any long-range order.

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

Dark matter substructure or source model systematics? A case study of cluster lens Abell S1063

Mapping the small-scale structure of the universe through gravitational lensing is a promising tool for probing the particle nature of dark matter. Curved Arc Basis (CAB) has been proposed as a local lensing formalism in galaxy clusters, with the potential to detect low-mass dark matter substructure. In this work, we analyse the cluster lens Abell S1063 in search of dark matter substructure with the CAB formalism, using multiband imaging data from James Webb Space Telescope ( JWST ). We use two different source modelling methods: shapelets and pixel-based source reconstruction based on Delaunay triangulation. We find that source modelling systematics from shapelets result in a disagreement between CAB parameters measured from different filters. Source modelling with Delaunay significantly alleviates this systematic, as seen in the improvement in agreement across filters. We also find that inadequate complexity in source modelling can result in convincing spurious detections of dark matter substructure from strong gravitational lenses, as seen by our $\Delta \text{BIC} > 20$ measurement of a $M \sim 10^{10}$ ${\rm M}_{\odot }$ subhalo with shapelets, a spurious detection that is not reproduced with Delaunay source modelling. We demonstrate that multiband analysis with different JWST filters is key for disentangling source and lens model systematics from dark matter substructure detections.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Ion-specific clustering of metal-amphiphile complexes in rare earth separations

The nanoscale structure of a complex fluid can play a major role in the selective adsorption of ions at the nanometric interfaces, which is crucial in industrial and technological applications. Here we study the effect of anions and lanthanide ions on the nanoscale structure of a complex fluid formed by metal-amphiphile complexes, using small angle X-ray scattering. The nano- and mesoscale structures we observed can be directly connected to the preferential transfer of light (La and Nd) or heavy (Er and Lu) lanthanides into the complex fluid from an aqueous solution. While toluene-based complex fluids containing trioctylmethylammonium-nitrate (TOMA-nitrate) always show the same mesoscale hierarchical structure regardless of lanthanide loading and prefer light lanthanides, those containing TOMA-thiocyanate show an evolution of the mesoscale structure as a function of the lanthanide loading and prefer heavy lanthanides. The hierarchical structure indicates the presence of attractive interactions between ion-amphiphile aggregates, causing them to form clusters. A clustering model that accounts for the hard sphere repulsions and short-range attractions between the aggregates has been adapted to model the X-ray scattering results. The new model successfully describes the nanoscale structure and helps in understanding the mechanisms responsible for amphiphile assisted ion transport between immiscible liquids. Accordingly, our results imply different mechanisms of lanthanide transport depending on the anion present in the complex fluid and correspond with anion-dependent trends in rare earth separations.

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

Reactivity, Mechanism, and Assembly of the Alternative Nitrogenases

Biological nitrogen fixation is catalyzed by the enzyme nitrogenase, which facilitates the cleavage of the relatively inert triple bond of N 2 . Nitrogenase is most commonly associated with the molybdenum–iron cofactor called FeMoco or the M-cluster, and it has been the subject of extensive structural and spectroscopic characterization over the past 60 years. In the late 1980s and early 1990s, two “alternative nitrogenase” systems were discovered, isolated, and found to incorporate V or Fe in place of Mo. These systems are regulated by separate gene clusters; however, there is a high degree of structural and functional similarity between each nitrogenase. Limited studies with the V- and Fe-nitrogenases initially demonstrated that these enzymes were analogously active as the Mo-nitrogenase, but more recent investigations have found capabilities that are unique to the alternative systems. In this review, we will discuss the reactivity, biosynthetic, and mechanistic proposals for the alternative nitrogenases as well as their electronic and structural properties in comparison to the well-characterized Mo-dependent system. Studies over the past 10 years have been particularly fruitful, though key aspects about V- and Fe-nitrogenases remain unexplored.

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

The Ellipticity of Galaxy Clusters at a Large Radius

Galaxy clusters are the largest known gravitationally bound structures in the universe, consisting of hundreds to thousands of galaxies (Figure 1). Dark matter contributes the majority of mass to galaxy clusters, and therefore has a strong influence on the arrangement of member galaxies. By determining the shape of galaxy clusters, we can figure out the shape of the dark matter, which is important for cosmology and galaxy formation studies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Hydrogen Evolution on Electrode‐Supported Pt n Clusters: Ensemble of Hydride States Governs the Size Dependent Reactivity

Abstract We report the size‐dependent activity and stability of supported Pt 1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters outperform polycrystalline Pt in activity, with size‐dependent stability. To understand the size effects, we use DFT calculations to study the structural fluxionality under varying potentials. We show that the clusters can reshape under H coverage and populate an ensemble of states with diverse stoichiometry, structure, and thus reactivity. Both experiment and theory suggest that electrocatalytic species are hydridic states of the clusters (≈2 H/Pt). An ensemble‐based kinetic model reproduces the experimental activity trend and reveals the role of metastable states. The stability trend is rationalized by chemical bonding analysis. Our joint study demonstrates the potential‐ and adsorbate‐coverage‐dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.

Zhang, Zisheng↗