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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 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Galactic Bar Resonances with Diffusion: An Analytic Model with Implications for Bar–Dark Matter Halo Dynamical Friction

Abstract The secular evolution of disk galaxies is largely driven by resonances between the orbits of “particles” (stars or dark matter) and the rotation of non-axisymmetric features (spiral arms or a bar). Such resonances may also explain kinematic and photometric features observed in the Milky Way and external galaxies. In simplified cases, these resonant interactions are well understood: for instance, the dynamics of a test particle trapped near a resonance of a steadily rotating bar is easily analyzed using the angle-action tools pioneered by Binney, Monari, and others. However, such treatments do not address the stochasticity and messiness inherent to real galaxies—effects that have, with few exceptions, been previously explored only with complex N -body simulations. In this paper, we propose a simple kinetic equation describing the distribution function of particles near an orbital resonance with a rigidly rotating bar, allowing for diffusion of the particles’ slow actions. We solve this equation for various values of the dimensionless diffusion strength Δ, and then apply our theory to the calculation of bar–halo dynamical friction. For Δ = 0, we recover the classic result of Tremaine and Weinberg that friction ultimately vanishes, owing to the phase mixing of resonant orbits. However, for Δ > 0, we find that diffusion suppresses phase mixing, leading to a finite torque. Our results suggest that stochasticity—be it physical or numerical—tends to increase bar–halo friction, and that bars in cosmological simulations might experience significant artificial slowdown, even if the numerical two-body relaxation time is much longer than a Hubble time.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Chemical Understanding of Actinide Separations

This work provides a broad overview of the separation processes used to isolate actinides and the experimentally and computationally determined chemical characteristics that define those separations. The redox chemistry of the actinides plays a pivotal role in both aqueous and pyrochemical processing separations. The near-overlapping energies of the 6d and 5f orbitals in the light actinides allow for facile adjustment of actinide oxidation states, which is used in many established separation methods. In contrast, the stable, generally 3+ oxidation states of the mid- and heavy actinides can make it difficult to separate them from the similarly lanthanides(III). In aqueous separations, the tendency of the actinides to form anionic and neutral aqueous complexes with a variety of complexants (especially soft donors) is used to achieve high separation factors between chemically similar elements in both solid–liquid separations and liquid–liquid extraction. This selectivity can be further tuned through the use of specialized organic or solid-phase ligands. Pyroprocessing separations utilize the unique redox behavior of the actinides to adjust their distribution between a molten salt electrolyte and either a solid electrode or molten metal phase. Atomic-level insights into the mechanisms underlying actinide separation processes, with the ultimate goal of predicting separation behavior, can be provided by electronic structure and statistical mechanical-based calculation methods.

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

An Ion-Imprinting Derived Strategy to Synthesize Single-Atom Iron Electrocatalysts for Oxygen Reduction

Carbon-based single-atom catalysts (CSACs) have recently received extensive attention in catalysis research. However, the preparation process of CSACs involves a high-temperature treatment, during which metal atoms are mobile and aggregated into nanoparticles, detrimental to the catalytic performance. Herein, an ion-imprinting derived strategy is proposed to synthesize CSACs, in which isolated metal-nitrogen-carbon (Me-N 4 -C x ) moiety covalently binds oxygen atoms in Si-based molecular sieve frameworks. Such a feature makes Me-N 4 -C x moiety well protected/confined during the heat treatment, resulting in the final material enriched with single-atom metal active sites. As a proof of concept, a single-atom Fe-N-C catalyst is synthesized by using this ion-imprinting derived strategy. Finally, experimental results and theoretical calculations demonstrate high concentration of single FeN 4 active sites distributed in this catalyst, resulting in an outstanding oxygen reduction reaction (ORR) performance with a half-wave potential of 0.908 V in alkaline media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Lattice Disorder and Oxygen Migration Pathways in Pyrochlore and Defect-Fluorite Oxides

Atomic-scale disorder plays an important role in the chemical and physical properties of oxide materials. The structural flexibility of pyrochlore-type oxides allows for crystal-chemical engineering of these properties. Compositional modification can push pyrochlore oxides toward a disordered defect-fluorite structure with anion Frenkel pair defects that facilitate oxygen migration. The local structure of the long-range average cubic defect-fluorite was recently claimed to consist of randomly arranged orthorhombic weberite-type domains. Here, we show, using low-temperature neutron total-scattering experiments, that this is not the case for Zr-rich defect-fluorites. By analyzing data from the pyrochlore/defect-fluorite Y 2 Sn 2–x Zr x O 7 series using a combination of neutron pair distribution function and big-box modelling, we have differentiated and quantified the relationship between anion sub-lattice disorder and Frenkel defects. These details directly influence the energy landscape for oxygen migration and are crucial for simulations and design of new materials with improved properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

First-Principles Simulations of CuCl in High-Temperature Water Vapor

Experimental data suggest that the solubility of copper in high-temperature water vapor is controlled by the formation of hydrated clusters of the form CuCl(H 2 O) n , where the average number of water molecules in the cluster generally increases with increasing density [Migdisov, A. A.; et al. Geochim. Cosmochim. Acta2014, 129, 33–53]. However, the precise nature of these clusters is difficult to probe experimentally. Moreover, there are some discrepancies between experimental estimates of average cluster size and prior simulation work [Mei, Y. Geofluids2018, 2018, 4279124]. Here, we have performed first-principles Monte Carlo (MC) and molecular dynamics (MD) simulations to explore these clusters in finer detail. We find that molecular dynamics is not the most appropriate technique for studying aggregation in vapor phases, even at relatively high temperatures. Specifically, our MD simulations exhibit substantial problems in adequately sampling the equilibrium cluster size distribution. In contrast, MC simulations with specialized cluster moves are able to accurately sample the phase space of hydrogen-bonding vapors. At all densities, we find a stable, slightly distorted linear H 2 O–Cu–Cl structure, which is in agreement with the earlier simulations, surrounded by a variable number of water molecules. The surrounding water molecules do not form a well-defined second solvation shell but rather a loose network of hydrogen-bonded water with molecular CuCl on the outside edge of the water cluster. We also find a broad distribution of hydration numbers, especially at higher densities. In contrast to previous simulation work but in agreement with experimental data, we find that the average hydration number substantially increases with increasing density. Moreover, the value of the hydration number depends on the choice of cluster definition.

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

Synthesis of platinum nanoparticles on strontium titanate nanocuboids via surface organometallic grafting for the catalytic hydrogenolysis of plastic waste

Pt/SrTiO 3 (Pt/STO), prepared on small scale by atomic layer deposition (ALD), is a capable heterogeneous catalyst for the selective hydrogenolysis of polyolefins to hydrocarbon oils, providing a promising approach for upcycling plastic waste. However, because deposition by ALD is costly and resource-intensive, a new synthesis of Pt/STO is needed to effectively scale catalyst production and pursue the commercialization of upcycling processes. To that effect, this work details a scalable deposition method for Pt/STO made by surface organometallic chemistry (SOMC) techniques using Pt(II) acetylacetonate or and trimethyl(methylcyclopentadienyl)platinum. The STO support was calcined (550 °C), treated with ozone (200 °C), and finally steamed (200 °C) to afford a clean STO surface populated with only hydroxyl groups. Pt precursors were dissolved in toluene and deposited onto STO. After reduction at 300 °C, the STO support was decorated with 1.0–1.5 nm Pt nanoparticles. The size and loading of these nanoparticles were varied by employing a multi-cycle deposition and oxidation and/or reduction process designed to ALD techniques. In conclusion, these Pt/STO catalysts hydrogenolyzed isotactic polypropylene into liquid products (>95% yield) with average molecular weights of 200–300 Da (~25 carbon atoms) and narrow size distributions at 300 °C and 180 psi H 2 .

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

Convergence acceleration of Monte Carlo many-body perturbation methods by direct sampling

In the Monte Carlo many-body perturbation (MC-MP) method, the conventional correlation-correction formula, which is a long sum of products of low-dimensional integrals, is first recast into a short sum of high-dimensional integrals over electron-pair and imaginary-time coordinates. These high-dimensional integrals are then evaluated by the Monte Carlo method with random coordinates generated by the Metropolis–Hasting algorithm according to a suitable distribution. The latter algorithm, while advantageous in its ability to sample nearly any distribution, introduces autocorrelation in sampled coordinates, which in turn increases the statistical uncertainty of the integrals and thus the computational cost. It also involves wasteful rejected moves and an initial “burn-in” step as well as displays hysteresis. Here, an algorithm is proposed that directly produces a random sequence of electron-pair coordinates for the same distribution used in the MC-MP method, which is free from autocorrelation, rejected moves, a burn-in step, or hysteresis. Furthermore, this direct-sampling algorithm is shown to accelerate second- (MC-MP2) and third-order Monte Carlo many-body perturbation (MC-MP3) calculations by up to 222% and 38%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Simultaneous thickness and thermal conductivity measurements of thinned silicon from 100 nm to 17 μm

Studies of size effects on thermal conductivity typically necessitate the fabrication of a comprehensive film thickness series. In this Letter, we demonstrate how material fabricated in a wedged geometry can enable similar, yet higher-throughput measurements to accelerate experimental analysis. Frequency domain thermoreflectance (FDTR) is used to simultaneously determine the thermal conductivity and thickness of a wedged silicon film for thicknesses between 100 nm and 17 μm by considering these features as fitting parameters in a thermal model. FDTR-deduced thicknesses are compared to values obtained from cross-sectional scanning electron microscopy, and corresponding thermal conductivity measurements are compared against several thickness-dependent analytical models based upon solutions to the Boltzmann transport equation. Our results demonstrate how the insight gained from a series of thin films can be obtained via fabrication of a single sample.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structural analysis of the catalytic domain of Artemis endonuclease/SNM1C reveals distinct structural features

The endonuclease Artemis is responsible for opening DNA hairpins during V(D)J recombination and for processing a subset of pathological DNA double-strand breaks. Artemis is an attractive target for the development of therapeutics to manage various B cell and T cell tumors, because failure to open DNA hairpins and accumulation of chromosomal breaks may reduce the proliferation and viability of pre-T and pre-B cell derivatives. However, structure-based drug discovery of specific Artemis inhibitors has been hampered by a lack of crystal structures. Here, we report the structure of the catalytic domain of recombinant human Artemis. The catalytic domain displayed a polypeptide fold similar overall to those of other members in the DNA cross-link repair gene SNM1 family and in mRNA 3'-end-processing endonuclease CPSF-73, containing metallo-β-lactamase and β-CASP domains and a cluster of conserved histidine and aspartate residues capable of binding two metal atoms in the catalytic site. As in SNM1A, only one zinc ion was located in the Artemis active site. However, Artemis displayed several unique features. Unlike in other members of this enzyme class, a second zinc ion was present in the β-CASP domain that leads to structural reorientation of the putative DNA-binding surface and extends the substrate-binding pocket to a new pocket, pocket III. Moreover, the substrate-binding surface exhibited a dominant and extensive positive charge distribution compared with that in the structures of SNM1A and SNM1B, presumably because of the structurally distinct DNA substrate of Artemis. The structural features identified here may provide opportunities for designing selective Artemis inhibitors.

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

Acid-Base Equilibrium and Dielectric Environment Regulate Charge in Supramolecular Nanofibers

Peptide amphiphiles are a class of molecules that can self-assemble into a variety of supramolecular structures, including high-aspect-ratio nanofibers. It is challenging to model and predict the charges in these supramolecular nanofibers because the ionization state of the peptides are not fixed but liable to change due to the acid-base equilibrium that is coupled to the structural organization of the peptide amphiphile molecules. Here, we have developed a theoretical model to describe and predict the amount of charge found on self-assembled peptide amphiphiles as a function of pH and ion concentration. In particular, we computed the amount of charge of peptide amphiphiles nanofibers with the sequence C 16 − V 2 A 2 E 2 . In our theoretical formulation, we consider charge regulation of the carboxylic acid groups, which involves the acid-base chemical equilibrium of the glutamic acid residues and the possibility of ion condensation. The charge regulation is coupled with the local dielectric environment by allowing for a varying dielectric constant that also includes a position-dependent electrostatic solvation energy for the charged species. We find that the charges on the glutamic acid residues of the peptide amphiphile nanofiber are much lower than the same functional group in aqueous solution. There is a strong coupling between the charging via the acid-base equilibrium and the local dielectric environment. Our model predicts a much lower degree of deprotonation for a position-dependent relative dielectric constant compared to a constant dielectric background. Furthermore, the shape and size of the electrostatic potential as well as the counterion distribution are quantitatively and qualitatively different. These results indicate that an accurate model of peptide amphiphile self-assembly must take into account charge regulation of acidic groups through acid–base equilibria and ion condensation, as well as coupling to the local dielectric environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A mathematical framework for ejecta cloud dynamics with application to source models and piezoelectric mass measurements

We present a mathematical framework for describing the dynamical evolution of an ejecta cloud generated by a generic ejecta source model. We consider a piezoelectric sensor fielded in the path of an ejecta cloud, for experimental configurations in which the ejecta are created at a singly shocked planar surface and fly ballistically through vacuum to the stationary sensor. To do so, we introduce the concept of a time- and velocity-dependent ejecta “areal mass function.” We derive expressions for the analytic (“true”) accumulated ejecta areal mass at the sensor and the measured (“inferred”) value obtained via the standard method for analyzing piezoelectric voltages. In this way, we derive an exact expression and upper bound for the error imposed upon a piezoelectric ejecta mass measurement (in a perfect system) by the assumption of instantaneous creation, which is commonly required for momentum diagnostic analyses. This error term is zero for truly instantaneous source models; otherwise, the standard piezoelectric analysis is guaranteed to overestimate the true mass. When combined with a piezoelectric dataset, this framework provides a unique solution for the ejecta particle velocity distribution, subject to the assumptions inherent in the data analysis. The framework also leads to strong boundary conditions that any ejecta source model must satisfy in order to be consistent with apparently global properties of piezoelectric measurements from a wide range of experiments. We demonstrate this methodology by applying it to the Richtmyer–Meshkov instability+self-similar velocity distribution ejecta source model currently under development at Los Alamos National Laboratory.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Accurate localization of Kosterlitz-Thouless-type quantum phase transitions for one-dimensional spinless fermions

We investigate the charge-density wave (CDW) transition for one-dimensional spinless fermions at half band filling with nearest-neighbor electron transfer amplitude t and interaction V. The model is equivalent to the anisotropic XXZ Heisenberg model for which the Bethe Ansatz provides an exact solution. For V>V c =2t, the CDW order parameter and the single-particle gap are finite but exponentially small, as is characteristic for a Kosterlitz-Thouless transition. It is notoriously difficult to locate such infinite-order phase transitions in the phase diagram using approximate analytical and numerical approaches. Second-order Hartree-Fock theory is qualitatively applicable for all interaction strengths, and predicts the CDW transition to occur at V$^{(2)}_{c,2}$≈1.5t. Second-order Hartree Fock theory is almost variational because the density of quasiparticle excitations is small. We apply the density-matrix renormalization group (DMRG) for periodic boundary conditions for system sizes up to 514 sites, which permits a reliable extrapolation of all physical quantities to the thermodynamic limit, apart from the critical region. We investigate the ground-state energy, the gap, the order parameter, the momentum distribution, the quasiparticle density, and the density-density correlation function to locate V c from the DMRG data. In conclusion, tracing the breakdown of the Luttinger liquid and the peak in the quasiparticle density at the band edge permits us to reproduce V c with an accuracy of one percent.

1-dimensional spin chains↗
DOE OSTI2025

A digital twin platform for building performance monitoring and optimization: Performance simulation and case studies

Advancements in sensor technology, data analytics, affordable compute, and communication infrastructure have paved the way for Digital Twin technology in optimizing building operations and controls. This study presents the development of an open and interoperable web-based Digital Twin platform for integrating diverse data streams and facilitating effective user interactions. The platform utilizes modern technologies for the web framework and time-series data management, ensuring scalability and responsiveness. The backend supports seamless integration of diverse data sources and emulators, incorporating data from building sensors and meters, external weather Application Programming Interfaces, and advanced EnergyPlus simulation models of the building and its energy systems including the Distributed Energy Resources that are formulated in Functional Mockup Units. A simulation case study was conducted with FlexLab, a test facility on Lawrence Berkeley National Laboratory campus. The case study includes normal operations, Distributed Energy Resource integration, and power outage scenarios, to illustrate the Digital Twin’s ability to provide critical insights into energy performance and thermal resilience. The results demonstrated the platform’s potential as a decision-support tool for optimizing building energy performance and enhancing resilience against extreme weather events. Future work will focus on deploying the Digital Twin platform to a real building for field validation, extending its capabilities to cover more scenarios such as bidirectional Electric Vehicle interactions, and enhancing user engagement.

EnergyPlus↗
DOE OSTI2023

MALDI-MS screening of microbial colonies with isomer resolution to select fatty acid desaturase variants

Creating controlled lipid unsaturation locations in oleochemicals can be a key to many bioengineered products. However, evaluating the effects of modifications to the acyl-ACP desaturase on lipid unsaturation is not currently amenable to high-throughput assays, limiting the scale of redesign efforts to <200 variants. Here, we report a rapid MS assay for profiling the positions of double bonds on membrane lipids produced by Escherichia coli colonies after treatment with ozone gas. By MS measurement of the ozonolysis products of Δ6 and Δ8 isomers of membrane lipids from colonies expressing recombinant Thunbergia alata desaturase, we screened a randomly mutagenized library of the desaturase gene at 5 s per sample. Two variants with altered regiospecificity were isolated, indicated by an increase in 16:1 Δ8 proportion. We also demonstrated the ability of these desaturase variants to influence the membrane composition and fatty acid distribution of E. coli strains deficient in the native acyl-ACP desaturase gene, fabA. Lastly, we used the fabA deficient chassis to concomitantly express a non-native acyl- ACP desaturase and a medium-chain thioesterase from Umbellularia californica, demonstrating production of only saturated free fatty acids.

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

Symbiotic bacteriophages exhibit multiple adaptive strategies in activated sludge flocs and contribute to floc stability

Despite the importance of phages for the dynamics and functions of microbial communities, it remains largely unexplored how symbiotic phages adapt in activated sludge systems and influence microbial aggregate stability, which is critical for clarification and reliable performance. Here, based on 12,127 phage contigs recovered from 12 activated sludge microbiomes, the symbiotic phages exhibited broad host ranges and infected dominant prokaryotes in activated sludge. Moreover, these phage communities exhibited high lysogenicity (49% to 66% lysogenic phages) and harbored diverse auxiliary metabolic genes (AMGs) that could enhance microbial aggregate stability, such as genes coding for lipopolysaccharide, peptidoglycan, and extracellular polysaccharide biosynthesis. Additionally, prokaryotic antiviral systems were widely distributed in dominant prokaryotes, particularly the Restriction-Modification (RM) and CRISPR-Cas systems, which could mitigate potential harmful phage infections. Overall, this study reveals the contemporary beneficial relationship between phages and prokaryotic hosts in activated sludge microbiomes and the potential benefits of symbiotic phages on floc stability.

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

Probing Electrolyte Influence on CO 2 Reduction in Aprotic Solvents

Selective CO 2 capture and electrochemical conversion are important tools in the fight against climate change. Industrially, CO 2 is captured using a variety of aprotic solvents due to their high CO 2 solubility. However, most research efforts on electrochemical CO 2 conversion use aqueous media and are plagued by competing hydrogen evolution reaction (HER) from water breakdown. Fortunately, aprotic solvents can circumvent HER, making it important to develop strategies that enable integrated CO 2 capture and conversion. However, the influence of ion solvation and solvent selection within nonaqueous electrolytes for efficient and selective CO 2 reduction is unclear. In this work, we show that the bulk solvation behavior within the nonaqueous electrolyte can control the CO2 reduction reaction and product distribution occurring at the catalyst-electrolyte interface. We study different tetrabutylammonium (TBA) salts in two electrolyte systems with glyme ethers (e.g., 1,2 dimethoxyethane or DME) and dimethyl sulfoxide (DMSO) as a low and high dielectric constant medium, respectively. Using spectroscopic tools, we quantify the fraction of ion pairs that forms within the electrolyte. Also, we show how ion pair formation is prevalent in DME and is dependent on the anion type. More importantly, we show that as ion pair formation decreases within the electrolyte, CO 2 current densities increase, and a higher CO Faradaic efficiency is observed at low overpotentials. Meanwhile, in an electrolyte medium where the ion pair fraction does not change with the anion type (such as in DMSO), a smaller influence of solvation is observed on CO 2 current densities and product distribution. By directly coupling bulk solvation to interfacial reactions and product distribution, we showcase the importance and utility of controlling the reaction microenvironment in tuning the electrocatalytic reaction pathways. Insights gained from this work will enable novel electrolyte designs for efficient and selective CO 2 conversion to desired fuels and chemicals.

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

Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

The role of counterions in molecular recognition of lanthanides is underexplored, especially when they exhibit weak interactions with the metal cations. Here, we report a complementary and comprehensive investigation integrating theoretical calculations with X-ray absorption fine structure spectroscopy, dynamic light scattering, and small-angle X-ray scattering to reveal atomic-scale structural features beyond the immediate coordination sphere of a system used for rare-earth element separations. Here, our results indicate the formation of an unusual T-shaped outer-sphere lanthanide complex, containing two ligands and two nitrate ions in the first coordination sphere, whereas the third nitrate is weakly coordinated and resides in the second shell. This unique structural arrangement causes inhomogeneous charge distribution, leading to self-assembly of the complexes into larger nanoclusters through sterically directed electrostatic interactions in the nonpolar medium. Our findings point to the importance of "noncoordinating" anions in defining the degree of supramolecular aggregation and ion cluster assembly.

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

Solid-State Ionic Rectification in Perovskite Nanowire Heterostructures

Halide perovskites have attracted increasing research attention with regard to their potential for optoelectronic applications. Because of its low activation energy, ion migration is implicated in the long-term stability and many unusual transport behaviors of halide perovskite devices. However, direct observation and precise control of the ionic transport in halide perovskite crystals remain challenging. Here, we have designed an axial CsPbBr 3 -CsPbCl 3 nanowire heterostructure, in which electric-field-induced halide ion migration was clearly visualized and quantified. We demonstrated that halide ion migration is dependent on the applied electric field and exhibits ionic rectification in this solid-state system, which is due to the nonuniform distribution of the ionic vacancies in the nanowire that results from a competition between electrical screening and their creation/destruction at the electrodes' interfaces. Furthermore, the asymmetric heterostructure characteristics add an additional knob to control the ion movement in the design of advanced ionic circuits with halide perovskites as building blocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗