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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A Case Study of the Glycoside Hydrolase Enzyme Mechanism Using an Automated QM-Cluster Model Building Toolkit

Glycoside hydrolase enzymes are important for hydrolyzing the β-1,4 glycosidic bond in polysaccharides for deconstruction of carbohydrates. The two-step retaining reaction mechanism of Glycoside Hydrolase Family 7 (GH7) was explored with different sized QM-cluster models built by the Residue Interaction Network ResidUe Selector (RINRUS) software using both the wild-type protein and its E217Q mutant. The first step is the glycosylation, in which the acidic residue 217 donates a proton to the glycosidic oxygen leading to bond cleavage. In the subsequent deglycosylation step, one water molecule migrates into the active site and attacks the anomeric carbon. Residue interaction-based QM-cluster models lead to reliable structural and energetic results for proposed glycoside hydrolase mechanisms. The free energies of activation for glycosylation in the largest QM-cluster models were predicted to be 19.5 and 31.4 kcal mol −1 for the wild-type protein and its E217Q mutant, which agree with experimental trends that mutation of the acidic residue Glu217 to Gln will slow down the reaction; and are higher in free energy than the deglycosylation transition states (13.8 and 25.5 kcal mol −1 for the wild-type protein and its mutant, respectively). For the mutated protein, glycosylation led to a low-energy product. This thermodynamic sink may correspond to the intermediate state which was isolated in the X-ray crystal structure. Hence, the glycosylation is validated to be the rate-limiting step in both the wild-type and mutated enzyme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Correlations in cosmic density fields

A method is proposed to place constraints on the functional form of the high-order correlation functions zeta(sub n) that arise in cosmic density fields at large scales. This technique is based on a mass-in-cell statistic and a difference of mass in partitions of a cell. The relationship between these measures is sensitive to the formal structure of the zeta(sub n) as well as their amplitudes. This relationship is quantified in several theoretical models of structure, based on the hierarchical clustering paradigm. The results lead to a test for specific types of hierarchical clustering that is sensitive to correlations of all orders. The method is applied to examples of simulated large-scaled structure dominated by cold dark matter. In the preliminary study, the hierarchical paradigm appears to be a realistic approximation over a broad range of the scales. Furthermore, there is evidence that graphs of low-order vertices are dominant. On the basis of simulated data a phenomological model is specified that gives a good representation of clustering from linear scales to the strongly clustered regime (zeta(sub 2) approximately 500).

Bromley, B. C.↗
DOE OSTI2026

Dara: Automated Multiple-Hypothesis Phase Identification and Refinement from Powder X-ray Diffraction

Powder X-ray diffraction (XRD) is a foundational technique for characterizing crystalline materials. However, the reliable interpretation of XRD patterns, particularly in multiphase systems, remains a manual and expertise-demanding task. As a characterization method that only provides structural information, multiple reference phases can often be fit to a single pattern, leading to potential misinterpretation when alternative solutions are overlooked. To ease humans’ efforts and address the challenge, we introduce Dara (data-driven automated Rietveld analysis), a framework designed to automate the robust identification and refinement of multiple phases from powder XRD data. Dara performs an exhaustive tree search over all plausible phase combinations within a given chemical space and validates each hypothesis using the BGMN Rietveld refinement routine. Key features include structural database filtering, automatic clustering of isostructural phases during tree expansion, and peak-matching-based scoring to identify promising phases for refinement. When ambiguity exists, Dara generates multiple hypothesis which can then be decided between by human experts or with further characterization tools. By enhancing the reliability and accuracy of phase identification, Dara enables scalable analysis of realistic complex XRD patterns and provides a foundation for integration into multimodal characterization workflows, moving toward fully self-driving materials discovery.

Biological databases↗
NASA NTRS1983

X-ray observations of the southern cluster CA 0340-538 and the Horologium supercluster

X-ray observations of the Horologium supercluster are examined. Results show that the optically Coma-like cluster CA 0340-538 has a smooth X-ray structure which also resembles that of Coma. The density structure of its X-ray emitting gas, determined in a model-independent way, is found to be remarkably featureless, being consistent with a nearly isothermal polytrope out to approximately 2 Mpc from the cluster center. The total mass of the gas is determined to exceed 10% of the cluster virial mass and may contribute a substantial fraction of the cluster binding mass. Although CA 0329-527 is found to be an X-ray double cluster, its structure appears to be confused. CA 0325-539 is found to show no substantial X-ray emission. An upper limit of 1.3 x 10 to the 44th erg/s is determined for any diffuse 2-10 keV emission from the Horologium supercluster.

Ku, W. H.-M.↗
DOE OSTI2020

Crystal Structure and Atomic Vacancy Optimized Thermoelectric Properties in Gadolinium Selenides

Thermoelectric materials enable the energy conversion of waste heat into electricity, helpful to relieve global energy crisis. Here, we report a systematic investigation on high-temperature thermoelectric gadolinium selenides, cubic Gd 3-x Se 4 (x = 0.16, 0.21 and 0.25) and orthorhombic Gd 2 Se 3-y (y = 0.02, 0.06 and 0.08). High energy synchrotron x-ray diffraction and total scattering have been used to investigate the crystallographic and local structures. Atomic-scale clusters of Gd vacancy in the cubic phase are observed by employing the reverse Monte Carlo simulation. For cubic Gd 3-x Se 4 , adjusting Gd vacancy triggers the effect of multiple conduction bands, confirmed by the increase in effective masses and theoretical calculations. A reasonable peak zT value of 0.27 is achieved at 850 K for Gd 3-x Se 4 (x = 0.16). On the other hand, tuning Se vacancy enables the optimization of electron concentration for the orthorhombic Gd 2 Se 3-y . More significantly, its low deformation potential (Ξ = 12eV) gives rise to enhanced electron mobility and higher peak zT value of 0.54 at 850 K for Gd 2 Se 3-y (y = 0.02). Intriguingly, a higher zT of 1.2 at 1200 K is reasonably predicted by quality factor analysis. Finally, this work extends the scope of high-temperature thermoelectric materials and facilitates the exploration of novel high-temperature thermoelectric materials

36 MATERIALS SCIENCE↗
DOE OSTI2024

Intrinsic Bonding and Reactivity of Actinide Clusters Poster

The effect of electronic structure on chemical bonding and reactivity is one of the most important questions in the field of chemistry. Insight into chemical bond formation involving elements that contain f electrons (i.e., the lanthanides and actinides) is critical for solving specific technical challenges, such as development of advanced nuclear fuel cycles and efficient rare earth separations, as well as a broader understanding of bonding across the entire periodic table. The primary technique for studying the fundamentals of lanthanide and actinide bonding is crystallization of metal-ligand compounds followed by structural determination with X-rays and comparison to theory with computational chemistry. While this procedure has yielded significant insights for a wide variety of elements, it is challenging to apply to the heavier trans-uranic actinides such as berkelium and californium because of limited material availability, significant radioactivity, and poorly understood chemical reactivity of these elements. We hypothesize that by forming actinide-ligand clusters in a mass spectrometer and probing their reactivity in the gas-phase, many of the challenges associated with studying the heavier trans-uranic elements can be circumvented. This project will develop a capability to address a wide range of actinide bonding and reactivity phenomena, increasing Idaho National Laboratory’s capability to address fundamental questions at the forefront of heavy element chemical and molecular science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Paramagnetic Attraction of Impurity-Helium Solids

Impurity-helium solids are formed when a mixture of impurity and helium gases enters a volume of superfluid helium. Typical choices of impurity gas are hydrogen deuteride, deuterium, nitrogen, neon and argon, or a mixture of these. These solids consist of individual impurity atoms and molecules as well as clusters of impurity atoms and molecules covered with layers of solidified helium. The clusters have an imperfect crystalline structure and diameters ranging up to 90 angstroms, depending somewhat on the choice of impurity. Immediately following formation the clusters aggregate into loosely connected porous solids that are submerged in and completely permeated by the liquid helium. Im-He solids are extremely effective at stabilizing high concentrations of free radicals, which can be introduced by applying a high power RF dis- charge to the impurity gas mixture just before it strikes the super fluid helium. Average concentrations of 10(exp 19) nitrogen atoms/cc and 5 x 10(exp 18) deuterium atoms/cc can be achieved this way. It shows a typical sample formed from a mixture of atomic and molecular hydrogen and deuterium. It shows typical sample formed from atomic and molecular nitrogen. Much of the stability of Im-He solids is attributed to their very large surface area to volume ratio and their permeation by super fluid helium. Heat resulting from a chance meeting and recombination of free radicals is quickly dissipated by the super fluid helium instead of thermally promoting the diffusion of other nearby free radicals.

Bernard, E. P.↗
DOE OSTI2022

Attosecond spectroscopy of size-resolved water clusters

Electron dynamics in water are of fundamental importance for a broad range of phenomena, but their real-time study faces numerous conceptual and methodological challenges. Here, in this paper, we introduce attosecond size-resolved cluster spectroscopy and build up a molecular-level understanding of the attosecond electron dynamics in water. We measure the effect that the addition of single water molecules has on the photoionization time delays of water clusters. We find a continuous increase of the delay for clusters containing up to four to five molecules and little change towards larger clusters. We show that these delays are proportional to the spatial extension of the created electron hole, which first increases with cluster size and then partially localizes through the onset of structural disorder that is characteristic of large clusters and bulk liquid water. These results indicate a previously unknown sensitivity of photoionization delays to electron-hole delocalization and indicate a direct link between electronic structure and attosecond photoionization dynamics. Our results offer new perspectives for studying electron-hole delocalization and its attosecond dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

Transport of Light Ions in Matter

A recent set of light ion experiments are analyzed using the Green's function method of solving the Boltzmann equation for ions of high charge and energy (the GRNTRN transport code) and the NUCFRG2 fragmentation database generator code. Although the NUCFRG2 code reasonably represents the fragmentation of heavy ions, the effects of light ion fragmentation requires a more detailed nuclear model including shell structure and short range correlations appearing as tightly bound clusters in the light ion nucleus. The most recent NTJCFRG2 code is augmented with a quasielastic alpha knockout model and semiempirical adjustments (up to 30 percent in charge removal) in the fragmentation process allowing reasonable agreement with the experiments to be obtained. A final resolution of the appropriate cross sections must await the full development of a coupled channel reaction model in which shell structure and clustering can be accurately evaluated.

Wilson, J. W.↗
DOE OSTI2023

Boosting Hydrogen Evolution in Neutral Medium by Accelerating Water Dissociation with Ru Clusters Loaded on Mo 2 CTx MXene

Abstract Electrocatalytic hydrogen evolution reaction (HER) in mild neutral medium is a compelling goal for environmentally sustainable energy conversion, but its development is greatly limited by slow kinetics. Platinum group noble metals exhibit ultra‐high HER activities, but their scarcity and performance instability restrict wide application. Herein, taking advantage of excellent catalyst carrier properties of 2D‐layered transition metal carbides (MXenes), highly dispersed of Ru clusters anchored on Mo 2 CT x MXene are demonstrated as a superior HER electrocatalyst, which is prepared by a facile in situ reduction strategy. The as‐prepared Ru/Mo 2 CT x catalyst exhibits a very low overpotential of 73 mV to achieve a current density of −10 mA cm −2 and Tafel slope of 57 mV dec −1 in neutral medium, surpassing performance of most previously reported MXene‐based catalysts. In addition, Ru/Mo 2 CT x catalyst also presents superior stability compared to commercial Pt/C. Experimental results and theoretical calculations indicate that the interaction between Ru clusters modulates the electronic structure of active sites and promotes H 2 O dissociation and hydrogen desorption.

Wu, Yanze↗
DOE OSTI2025

Reversible CO 2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex

Abstract The authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir 3 H 6 ( μ 3 ‐H)(PN) 3 ] 2+ ( 2‐H , PN = (2‐pyridyl)CH 2 PBu t 2 ). Despite its unusual stability to unsaturated organics, electrophiles, and even CF 3 SO 3 D, they find that complex 2‐H catalyzes hydrogenation of CO 2 to formate (TON Ir = 9600) and reverse formic acid dehydrogenation (TON Ir = 54 400). The hydrogenation operates via a reactive intermediate [Ir 3 H 4 ( μ ‐H) 4 (PN) 3 ] + ( 5 ). Neutron crystallography and DFT‐supported neutron vibrational spectroscopy of 2‐H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir 3 H 7 core. Stoichiometric oxidation of 2‐H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra‐ and pentanuclear clusters [Ir 3 H 6 ( μ 3 ‐AuPPh 3 )(PN) 3 ] 2+ ( 2‐Au ) and [Ag{Ir 2 H 4 ( μ ‐OAc)(PN) 2 } 2 ] 3+ ( 6 ) are generated using AuPPh 3 + and AgOAc, respectively. Further oxidation to class [Ir 2 H 3 ( μ ‐X) 2 (PN) 2 ] + is possible with AgOAc, Hg(OAc) 2 , or I 2 . Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir 2 Cl 4 ( μ ‐Cl) 2 (PN) 2 ] ( 11 ).

Cherepakhin, Valeriy [Loker Hydrocarbon Research I↗
DOE OSTI2025

Reversible CO 2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex

Here, the authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir 3 H 6 (μ 3 -H)(PN) 3 ] 2+ (2-H, PN = (2-pyridyl)CH 2 PBu t 2 ). Despite its unusual stability to unsaturated organics, electrophiles, and even CF 3 SO 3 D, they find that complex 2-H catalyzes hydrogenation of CO 2 to formate (TON Ir = 9600) and reverse formic acid dehydrogenation (TON Ir = 54 400). The hydrogenation operates via a reactive intermediate [Ir 3 H 4 (μ-H) 4 (PN) 3 ] + (5). Neutron crystallography and DFT-supported neutron vibrational spectroscopy of 2-H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir 3 H 7 core. Stoichiometric oxidation of 2-H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra- and pentanuclear clusters [Ir 3 H 6 (μ 3 -AuPPh 3 )(PN) 3 ] 2+ (2-Au) and [Ag{Ir 2 H 4 (μ-OAc)(PN) 2 } 2 ] 3+ (6) are generated using AuPPh 3 + and AgOAc, respectively. Further oxidation to class [Ir 2 H 3 (μ-X) 2 (PN) 2 ] + is possible with AgOAc, Hg(OAc) 2 , or I 2 . Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir 2 Cl 4 (μ-Cl) 2 (PN) 2 ] (11).

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

Large-scale atomistic model construction of subbituminous and bituminous coals for solvent extraction simulations with reactive molecular dynamics

Large-scale atomistic models for complex polycyclic aromatic hydrocarbon systems help understand the chemical properties and behaviors of complex feedstocks such as coal or petroleum. However, the development and utilization of large-scale models remain limited due to the difficulty in achieving the varied structural characteristics necessary to capture stochastic nature of these feedstocks. Here we demonstrate a systematic workflow to construct stochastic molecular systems from a broad analytical suite: high-resolution transmission electron microscopy (HRTEM), carbon-13 nuclear magnetic resonance spectroscopy ( 13 C NMR), laser desorption ionization mass spectroscopy (LDI-MS), and elemental analysis. We present a model construction and analysis utility of a new Python-based module. We selected one subbituminous and three high-volatile bituminous coals to construct large-scale models (~40,000 atoms). The constructed models were utilized to examine the affinity for solvent extraction (naphthalene or tetralin) and the effect of structural properties (e.g., aromatic cluster size, functional groups, and cross-linking) in reactive molecular dynamics simulations. Complex chemical reactions were monitored with bond order transitions, intermediates formation, and mass distributions. Reactive molecular dynamics simulations suggest a plausible chemical extraction process and products for the complex fossil feedstocks. The results indicated that radical formations with bond breaking of bridging oxygens and carbons were required at high temperatures to facilitate hydrogeneration and extraction of gas molecules from radical-free molecules. We observed that aliphatic chains of tetralin were easily decomposed and combined with radicals to form small size of molecules with aryl bonding, mainly increasing molecules in the 500–1000 Da, while naphthalene had little impact on chemical extraction process.

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

A generalized and adaptable tensor-contraction-based cluster expansion formalism for multicomponent solids

Density functional theory (DFT)-based simulations of materials have first-principles accuracy, but are very computationally expensive. For simulating various properties of multi-component alloys, the cluster expansion (CE) technique has served as the standard workaround to improve computational efficiency. However, the standard CE technique is difficult to extend to exotic and/or low-symmetry lattices, often implemented via iteration over particular cluster types, which must be enumerated per lattice structure. In this work, we introduce the tensor cluster expansion (TCE), implemented in the open-source code tce-lib, which maps correlation functions to mixed tensor contractions, eliminating the need to iterate over cluster types and additionally making the calculation of correlation functions well-suited for massively parallel architectures like GPUs. We show that local interaction energies are an immediate consequence of the TCE formalism, yielding nearly $\mathcal{O}$(1) energy difference calculations. We then use this formalism to fit CE models for the TaW and CoNiCrFeMn systems, and use these models to respectively compute the enthalpy of mixing curve and Cowley short-range order parameters, showing excellent agreement with ground truth data.

Cluster expansion↗
DOE OSTI2022

Growth mechanism of glucose-based hydrochar under the effects of acid and temperature regulation

Improving the tailorability of hydrochar synthesis is an effective way to enhance its performance and utilization efficiency. In this study, the growth rate, morphology, and molecular structure of hydrochar were controlled by regulating the pH and temperature of the hydrothermal carbonization process. Growth process analysis indicates that hydrochar has three growth periods: induction, rapid, and stable growth periods. It is mainly controlled by 5-hydroxymethylfurfural (HMF), which is formed by converting glucose and its transformation products. Further, the regulation of acid can significantly shorten the induction period of hydrochar, even under low-temperature conditions (<180 °C), and increase the growth rate of hydrochar. However, the degree of hydrochar adhesion varies: the lower the temperature, the greater the degree of its adhesion. Molecular structural analysis demonstrates that hydrochar mainly consists of furan structural domains and aromatic clusters, and its surface is rich in oxygen-containing functional groups. The degree at which hydrochar was aromatized was improved by increasing the reaction temperature (160–220 °C); whereas the regulation of acid reduced it and increased the content of oxygen-containing functional groups on the hydrochar surface. Based on these results, it is proposed that hydrochar formation has five stages and three growth periods with or without acid regulation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Irradiation-induced chemical disordering in ceramics: The case of SiC

Chemical disordering is one feature of damage that occurs in irradiation environments and is common in ceramic compounds. This paper reviews irradiation-induced chemical disordering in SiC-based materials at elevated temperatures. Here the results were obtained using advanced analytical tools to characterize atomistic defects and to evaluate the chemistry of defect clusters and homonuclear bond structures. Finally, this paper demonstrates that chemical disordering is crucial to understanding microstructural stability and establishing a mechanistic modeling of microstructural evolution of irradiated SiC.

36 MATERIALS SCIENCE↗