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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Radiative Particle-in-Cell Simulations of Turbulent Comptonization in Magnetized Black-Hole Coronae

We report results from the first radiative particle-in-cell simulations of strong Alfvénic turbulence in plasmas of moderate optical depth. The simulations are performed in a local 3D periodic box and self-consistently follow the evolution of radiation as it interacts with a turbulent electron-positron plasma via Compton scattering. We focus on the conditions expected in magnetized coronae of accreting black holes and obtain an emission spectrum consistent with the observed hard state of Cyg X-1. Most of the turbulence power is transferred directly to the photons via bulk Comptonization, shaping the peak of the emission around 100 keV. The rest is released into nonthermal particles, which generate the MeV spectral tail. As a result, the method presented here shows promising potential for ab initio modeling of various astrophysical sources and opens a window into a new regime of kinetic plasma turbulence.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Molecular beam epitaxy of PdO on MgO (001)

PdO, widely used in catalysis in powder form for decades, has been predicted recently to be a Dirac semimetal. Synthesis of high-quality single crystals of this material is thus of great interest. Here, by using ozone-assisted molecular beam epitaxy, PdO thin films were grown on a MgO (001) substrate. X-ray diffraction and transmission electron microscopy indicate the film is a / b axis oriented, with the c axis lying in plane. Fully oxygenated PdO films have a low density of holelike carriers, and are insulating at the lowest temperatures. Our density functional theory calculations using the Heyd-Scuseria-Ernzerhof exchange-correlation functional suggest a ~1.0 eV band gap at the M point, where the gap can be reduced by tensile strain along the c axis and the bands begin to invert when the tensile strain is as high as 18%. Although tensile strain of this magnitude is experimentally not viable using epitaxy, electrons can be doped by oxygen reduction. Finally, our results emphasize the need for careful consideration of electron correlation effects and stoichiometry in ab initio modeling of topological semimetals involving transition metal oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Tuning band alignment at a semiconductor-crystalline oxide heterojunction via electrostatic modulation of the interfacial dipole

In this paper, we demonstrate that the interfacial dipole associated with bonding across the SrTiO 3 /Si heterojunction can be tuned through space charge, thereby enabling the band alignment to be altered via doping. Oxygen impurities in Si act as donors that create space charge by transferring electrons across the interface into SrTiO 3 . The space charge induces an electric field that modifies the interfacial dipole, thereby tuning the band alignment from type II to III. The transferred charge, accompanying built-in electric fields, and change in band alignment are manifested in electrical transport and hard x-ray photoelectron spectroscopy measurements. Ab initio models reveal the interplay between polarization and band offsets. We find that band offsets can be tuned by modulating the density of space charge across the interface. Modulating the interface dipole to enable electrostatic altering of band alignment opens additional pathways to realize functional behavior in semiconducting hybrid heterojunctions.

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

Transient electron scavengers modulate carrier density at a polar/nonpolar perovskite oxide heterojunction

Here, we show how transient electron scavengers can be utilized to control the carrier concentration at polar/non-polar perovskite interfaces. By combining quantitative synchrotron x-ray-based interface structure determination with ab initio modeling, we demonstrate that Nd vacancy formation and the resulting formation of Nd adatoms, stabilized by oxygen scavengers at the growth front, can quantitatively account for the decreased carrier concentration at the SrTiO 3 /n NdTiO 3 /SrTiO 3 (001) heterojunction for n = 1 unit cell. This study yields new insights into growth mechanisms and the effect of transient species and defects on the electronic properties of oxide heterojunctions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Surface termination control of charge transfer and band alignment across a semiconductor–crystalline-oxide heterojunction

Charge redistribution across heterojunctions has long been utilized to induce functional response in materials systems. Here we examine how the composition of the terminating surface affects charge transfer across a heterojunction consisting of Si and the crystalline complex oxide SrTiO 3 . Itinerant electrons in Si migrate across the interface toward the surface of SrTiO 3 due to surface depletion. The electron transfer in turn creates an electric field across the interface that modifies the interfacial dipole associated with bonding between SrTiO 3 and Si. The modification in the dipole leads to a change in band alignment, in which the conduction band of SrTiO 3 moves from being above the valence band of Si in energy, to below it. By capping the SrTiO 3 surface with ultrathin (≤ 1 nm) layers of BaO, SrO or TiO 2 , charge transfer across the interface can be weakened or inhibited. Ab initio modeling implicates the adsorption of oxygen associated with exposure to ambient conditions as driving the surface depletion in SrTiO 3 . In conclusion, the electronic coupling between the surface and buried interface expands the functionality of semiconductor-crystalline oxide heterojunctions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Bulk properties of honeycomb lattices of superconducting microwave resonators

We have realized different honeycomb lattices for microwave photons in the 4 to 8 GHz band using superconducting spiral resonators. Each lattice comprises a few hundred sites. Two designs have been studied, one leading to two bands touching at the Dirac points and one where a gap opens at the Dirac points. Using a scanning laser technique to image the eigenmodes of this new type of photonic lattices, we are able to reconstruct their band structure. The measured bands are in excellent agreement with ab initio models that combine numerical simulations of the electromagnetic properties of the spiral resonator and analytical calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Chemically tuned intermediate band states in atomically thin Cu x GeSe/SnS quantum material for photovoltaic applications

A new generation of quantum material derived from intercalating zerovalent atoms such as Cu into the intrinsic van der Waals gap at the interface of atomically thin two-dimensional GeSe/SnS heterostructure is designed, and their optoelectronic features are explored for next-generation photovoltaic applications. Advanced ab initio modeling reveals that many-body effects induce intermediate band (IB) states, with subband gaps (~0.78 and 1.26 electron volts) ideal for next-generation solar devices, which promise efficiency greater than the Shockley-Queisser limit of ~32%. The charge carriers across the heterojunction are both energetically and spontaneously spatially confined, reducing nonradiative recombination and boosting quantum efficiency. Using this IB material in a solar cell prototype enhances absorption and carrier generation in the near-infrared to visible light range. Tuning the active layer’s thickness increases optical activity at wavelengths greater than 600 nm, achieving ~190% external quantum efficiency over a broad solar wavelength range, underscoring its potential in advanced photovoltaic technology.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electron and Electron-Nuclear Dynamics of Open Quantum Subsystems

Leveraging an open-subsystem formulation of Density Functional Theory (DFT) we aim at describing periodic and molecular systems alike, including their electronic and nuclear dynamics. Subsystem DFT enables first principles simulations to approach realistic time- and length-scales, and most importantly sheds light on the dynamical behavior of complex systems. Taking subsystem DFT to the time domain allows us to inspect the electron dynamics of condensed-phase systems in real time. In liquids and interfaces, we observe all the relevant regimes proper of non-Markovian open quantum system dynamics, such as electronic energy transfer, and screening. In addition, the ab-initio modeling of system-bath interactions brought us to observe and justify the holographic time-dependent electron density theorem. Contrary to interactions between molecular (finite) systems, when molecules interact with metal or semiconductor surfaces the electron dynamics is strongly non-Markovian with dramatic repercussions to the molecule’s response to external perturbations. Metals and semiconductors typically have large polarizabilities, and even in a regime of low coupling their effect on impinging molecular species is significant–line broadening, peak shift, and intensity borrowing are observed, characterized, and explained in terms of inter-subsystem dynamical interactions and a many-body decomposition of the system’s density-density response function in a way that transcends the canons of Fermi Golden Rule.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

FY23 Progress Report on Viscosity and Thermal Conductivity Measurements of Molten Salts

As presented in this report, thermal conductivity and viscosity measurements were performed on key chloride pseudo-binary molten salt systems of relevance to molten salt reactor developers. Thermal conductivity measurements were conducted with a variable gap technique, in which a known heat flux is driven across a molten salt specimen and the temperature difference is measured, allowing calculation of the thermal conductivity. This is achieved by establishing a small gap between the bottom of a cylindrical inner containment, which houses electrical heating elements, and an outer containment, which houses cooling channels; the gap size can be varied by compression of a formed bellows. A new calibration scheme was developed herein, involving a correction factor to the heat flux based on He measurements at various temperatures. Furthermore, the data processing methodology was improved to minimize the impact of radiative heat transfer in the calculation of salt specimen thermal conductivity from the temperature difference measurements. Viscosity measurements were conducted with a rolling ball viscometer, in which a ball rolls some known distance in an angled tubular crucible, and the terminal velocity can be used to calculate the viscosity of the salt. The measurement can be performed in a quartz crucible, with which a standard camera can be used to track the ball, or in a metal crucible, with which x-ray radiography is required to track the ball. A new custom x-ray system was made and dedicated to the rolling ball viscometer to enable high throughput automated measurements with salts which require containment with metal. Both systems have been integrated with a ventilation stack which allows for off-gassing of radioactive material, enabling future measurements with U-bearing salts. The thermal conductivity measurements performed herein were with NaCl-KCl (44 mol% NaCl). This salt system was measured in the previous fiscal year, however the thermal conductivity values obtained were comparatively low, and so the system was remeasured with the aforementioned calibration scheme and improved post-processing techniques. The newly obtained thermal conductivity values for NaCl-KCl (44 mol% NaCl) indicate good agreement with kinetic theory and ab-initio models (within 5–10 %). The viscosity measurements performed herein were with three different compositions of NaCl-KCl: 75, 50, and 25 mol% NaCl; a new calibration scheme was applied to account for variable flow effects in the laminar regime. The results show reasonable agreement with literature (5–20 %, depending on the temperature, composition, and study); however, literature values are likely higher than true values based on pure end-member measurements performed in the comparative studies. The measurements conducted herein do show a trend such that viscosity increases with increasing NaCl concentration, which agrees well with one of two comparative studies. In general, the measurements conducted herein gives confidence in the capability to use these systems to accurately measure thermal conductivity and viscosity of actinide-bearing salts within the next fiscal year.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Computational and Experimental Investigation of Thermal-Mechanical- Chemical Mechanisms of High-burnup Spent Nuclear Fuel (SNF) Processes at Elevated Temperatures and Degradation Behavior in Geologic Repositories

The overarching goal of the combined computational and experimental R&D activities proposed in this project is to enhance understanding of the mechanisms and thermal-mechanical-chemical (TMC) parameters controlling the instant release fraction (IRF) and matrix dissolution of high-burnup (HB; burnup) spent nuclear fuels (SNFs) and the subsequent formation, stability, and phase transformations of SNF alteration products under long-term storage and geological disposal conditions. Uranium dioxide may undergo oxidative corrosion/alteration, and the IRF may be increased for HB SNF, both of which may affect environmental systems associated with SNF long-term storage and disposal. The oxidative matrix dissolution may form various complex uranyl-based phases, including a rich variety of oxides, silicates, carbonates and other secondary minerals in varied geological environments (e.g., studtite, metastudtite, amorphous uranyl peroxide, uranium trioxide, triuranium octoxide, schoepite, dehydrated schoepite, metaschoepite, becquerelite, soddyite, rutherfordine,...). These uranyl phases generally have higher mobility UO 2 +2 species than less soluble U 4+ phases. However, limited information on the thermodynamic properties and formation kinetics of these uranyl-bearing phases is available to predict explicitly paragenesis under the conditions relevant to long-term storage or disposal. The proposed project draws on complementary expertise and research backgrounds from the team members: (i) to apply a combined ab initio modeling (UNLV/UTEP and SNL) and experimental (UNLV) strategy investigating the high-temperature TMC mechanisms of alteration of SNF under α-radiolysis conditions; (ii) to investigate the mechanistic of phase transformations in UNF degradation products under various conditions expected in long-term storage systems (e.g. (UO 2 )O 2 (H 2 O) 4 → (UO 2 )O 2 (H 2 O) 2 → U 2 O 7 → UO 3 → U 3 O 8 ); (iii) to determine high-accuracy TMC parameters for complex uranyl-based phases formed in storage or geological disposal environments (e.g. UO 3 (H 2 O) 2 , Ca[(UO 2 ) 6 O 4 (OH) 8 ] 8 H 2 O, (UO 2 ) 2 (SiO 4 ) 3 2H 2 O,…). The unforeseen COVID-19 pandemic led to the laboratory/campus closure since March 2020, that resulted in a significant delay in reaching milestones in a satisfactory manner, due to (i) the statewide recommendation from stop-working to later limited work in the lab and work-from-home (WFH), (ii) no in-person interactions, and (iii) a hiring freeze at UNLV. Therefore, a no cost extension (10/01/2021- 9/30/2022) was requested to help make up the time we lost during the global pandemic in 2020-2021, leading to paradigm shifts in the focus of the project in the following three main tasks: Task 1 (Computational), Task 2 (Experimental), and Task 3 (Final report, due on 12/29/2022).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Understanding and Tailoring Diffusion and Co-Adsorption Inside the Confined Pores of Metal-Organic Frameworks (Final Scientific/Technical Report for Award DE-SC0019902)

The aim of this program was to gain a fundamental understanding of the behavior of various guest molecules in nano-confined environments, such as metal organic frameworks (MOFs), using a combination of novel synthesis, ab initio modeling, and in situ characterization. Through this project, we developed a concise understanding of the mechanisms that control adsorption/desorption of gaseous molecules and their mixtures, leading to design/synthesis guidelines for MOFs with desired functionality. We further developed methods to disentangle kinetic from thermodynamic effects during adsorption, as well as to characterize the interactions at play. In the first funding cycle, the focus was on the unambiguously characterization of co-adsorption and diffusion of gasses/vapors and their mixtures. In the second funding cycle, the focus was on characterizing the effects of the nano-confinement on the kinetics and thermodynamics of adsorption processes inside MOFs, again with an emphasis on mixtures of gasses and vapors. The nano-confinement can tip the thermodynamic vs. kinetic balance, and current understanding and theory based on single-component analysis can lead to incorrect predictions for mixtures. This is of particular interest in real-world applications, where gasses/vapors are typically mixed, contain impurities, or are often exposed to humid conditions. Our main findings were: (i) within confined environments the adsorption behavior of mixed gasses/vapors can be drastically different from the “sum” of the corresponding single phases; (ii) co-adsorption is often competitive and detrimental to performance, but it can also be cooperative and beneficial; (iii) in some co-adsorbed gasses/vapors, molecules that are strongly bound in the single-component phase can be replaced by molecules that are nominally weaker bound (molecular exchange) due to guest-guest interactions that lower the kinetic barriers and favor the final adsorption state; (iv) kinetic and thermodynamic effects can be precisely controlled through pore-size engineering and synthesis; and, (v) kinetic effects can be identified and disentangled from thermodynamic effects during adsorption through a series of sequential and simultaneous gas loading measurements. The short-term goal of this program was the controlling and understanding of common MOF systems in real-world situations where gasses/vapors are mixed, which will have an important impact on industrial processes and applications from gas storage and sequestration to catalysis and sensors. The long-term goals include the development of theoretical and experimental methods for gaining a fundamental understanding of adsorption/reaction processes within MOFs, as well as new guidelines for synthesizing MOFs with tailored physical and chemical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

H3O Radical in Proton-Exchange Membrane Fuel Cells and Its Role in Membrane Degradation

Based on previous experimental evidence on isotopic substitution, we postulate that the hydronium radical (H3O·) might be present in PEMFCs. Our ab initio modeling indicates that this radical can be stabilized by the sulfonic anion on the polymer sidechain, leading to a greatly reduced reaction barrier in the t-F degradation reaction with the assistance of explicit water by undergoing a sidechain conformational change. To our knowledge, this is the first evidence that H3O· could be present in electrochemical devices with both experimental and theoretical support.

fuel cell membrane degradation↗
DOE OSTI2024

Building an ab initio solvated DNA model using Euclidean neural networks

Accurately modeling large biomolecules such as DNA from first principles is fundamentally challenging due to the steep computational scaling of ab initio quantum chemistry methods. This limitation becomes even more prominent when modeling biomolecules in solution due to the need to include large numbers of solvent molecules. We present a machine-learned electron density model based on a Euclidean neural network framework that includes a built-in understanding of equivariance to model explicitly solvated double-stranded DNA. By training the machine learning model using molecular fragments that sample the key DNA and solvent interactions, we show that the model predicts electron densities of arbitrary systems of solvated DNA accurately, resolves polarization effects that are neglected by classical force fields, and captures the physics of the DNA-solvent interaction at the ab initio level.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Response functions and giant monopole resonances for light to medium-mass nuclei from the ab initio symmetry-adapted no-core–shell model

Using the ab initio symmetry-adapted no-core–shell model, we compute sum rules and response functions for light to medium-mass nuclei, starting from interactions that are derived in the chiral effective field theory. Specifically, we investigate electromagnetic transitions of monopole, dipole and quadrupole nature for 4 He, and explore dominant features of giant monopole resonances in symmetric nuclei such as the closed-shell 4 He and 16 O light nuclei, the intermediate-mass open-shell 20 Ne and the medium-mass closed-shell 40 Ca. Furthermore, for the NNLO opt chiral potential, we determine parameter-free monopole sum rules, which can provide information on the incompressibility of symmetric nuclear matter. Here, we report 213(10) MeV as an estimate for the compression modulus for infinite nuclear matter, which overlaps with the lower range of values often used in current astrophysical applications.

ab initio nuclear structure↗
DOE OSTI2021

Condensed Phase Water Molecular Multipole Moments from Deep Neural Network Models Trained on Ab Initio Simulation Data

Ionic solvation phenomena in liquids involve intense interactions in the inner solvation shell. For interactions beyond the first shell, the ion–solvent interaction energies result from the sum of many smaller-magnitude contributions that can still include polarization effects. Deep neural network (DNN) methods have recently found wide application in developing efficient molecular models that maintain near-quantum accuracy. In this work, we extend the DeePMD-kit code to produce accurate molecular multipole moments in the bulk and near interfaces. The new method is validated by comparing the DNN moments with those generated by ab initio simulations. The moments are used to compute the electrostatic potential at the center of a molecular-sized hydrophobic cavity in water. The results show that the fields produced by the DNN models are in quantitative agreement with the AIMD-derived values. These efficient methods will open the door to more accurate solvation models for large solutes such as proteins.

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

Nitromethane Decomposition via Automated Reaction Discovery and an Ab Initio Corrected Kinetic Model

In the explore the systematic construction of kinetic models from in silico reaction data for the decomposition of nitromethane. Our models are constructed in a computationally affordable manner by using reactions discovered through accelerated molecular dynamics simulations using the ReaxFF reactive force field. The reaction paths are then optimized to determine reaction rate parameters. We introduce a reaction barrier correction scheme that combines accurate thermochemical data from density functional theory with ReaxFF minimal energy paths. We validate our models across different thermodynamic regimes, showing predictions of gas phase CO and NO concentrations and high-pressure induction times that are similar to experimental data. The kinetic models are analyzed to find fundamental decomposition reactions in different thermodynamic regimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗