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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

Theoretical studies of diatomic and triatomic systems containing the group IB atoms Cu, Ag, and Au

Selected portions of the ground state potential energy surfaces of the Cu3, Ag3, AgCu2, and AuCu2 trimers are studied at the single-reference singles plus doubles configuration interaction and couple pair functional levels correlating 33 electrons. The calculations use the effective core potentials of Hay and Wadt (1985) to replace the deep core levels. The Cu3 and Ag3 molecules are found to have 2B2 obtuse-angled ground states, with low-lying 2A1 acute-angled excited states. The AgCu2 and AuCu2 molecules have 2A1 acute-angled ground states. The Cu3 molecule has a smaller 3d population than Ag3, and Cu3 has a smaller s electron density in the open-shell orbital than does Ag3, in agreement with recent ESR experiments.

Walch, Stephen P.↗
NASA NTRS2012

Kuang's Semi-Classical Formalism for Electron Capture Cross-Sections in Ion-Ion Collisions at Approximately to MeV/amu: Application to ENA Modeling

Recent discovery by STEREO A/B of energetic neutral hydrogen is spurring an interest and need for reliable estimates of electron capture cross sections at few MeVs per nucleon as well as for multi-electron ions. Required accuracy in such estimates necessitates detailed and involved quantum-mechanical calculations or expensive numerical simulations. For ENA modeling and similar purposes, a semi-classical approach offers a middle-ground approach. Kuang's semiclassical formalism to calculate electron-capture cross sections for single and multi-electron ions is an elegant and efficient method, but has so far been applied to limited and specific laboratory measurements and at somewhat lower energies. Our goals are to test and extend Kuang s method to all ion-atom and ion-ion collisions relevant to ENA modeling, including multi-electron ions and for K-shell to K-shell transitions.

Barghouty, A. F.↗
NASA NTRS2016

Outer Radiation Belt Dropout Dynamics Following the Arrival of Two Interplanetary Coronal Mass Ejections

Magnetopause shadowing and wave-particle interactions are recognized as the two primary mechanisms for losses of electrons from the outer radiation belt. We investigate these mechanisms, sing satellite observations both in interplanetary space and within the magnetosphere and particle drift modeling. Two interplanetary shocks sheaths impinged upon the magnetopause causing a relativistic electron flux dropout. The magnetic cloud (C) and interplanetary structure sunward of the MC had primarily northward magnetic field, perhaps leading to a concomitant lack of substorm activity and a 10 day long quiescent period. The arrival of two shocks caused an unusual electron flux dropout. Test-particle simulations have shown 2 to 5 MeV energy, equatorially mirroring electrons with initial values of L 5.5can be lost to the magnetosheath via magnetopause shadowing alone. For electron losses at lower L-shells, coherent chorus wave-driven pitch angle scattering and ULF wave-driven radial transport have been shownto be viable mechanisms.

Alves, L. R.↗
NASA NTRS2010

Simulation of Relativistic Shocks and Associated Self-Consistent Radiation for GRB Prompt Emission and Afterglows

Plasma instabilities excited in collisionless shocks are responsible for particle acceleration. We have investigated the particle acceleration and shock structure associated with an unmagnetized relativistic electron-positron jet propagating into an unmagnetized electron-positron plasma. Cold jet electrons are thermalized and slowed while the ambient electrons are swept up to create a partially developed hydrodynamic-like shock structure. In the leading shock, electron density increases by a factor of about 3.5 in the simulation frame. Strong electromagnetic fields are generated in the trailing shock and provide an emission site. This simulation corresponds to a case for gamma-ray burst afterglows. We will simulate colliding shells as an internal shock model for prompt emission. Turbulent magnetic fields generated by a slower shell will be collided by a faster shell. These magnetic fields contribute to the electron s transverse deflection behind the shock. We calculate the radiation from deflected electrons in the turbulent magnetic fields. The properties of this radiation may be important to understanding the complex time evolution and/or spectral structure in gamma-ray bursts

Nishikawa, Ken-Ichi↗
DOE OSTI2024

Density Functional Tight-Binding Models for Band Structures of Transition-Metal Alloys and Surfaces across the d -Block

First-principles electronic structure simulations are an invaluable tool for understanding chemical bonding and reactions. While machine-learning models such as interatomic potentials significantly accelerate the exploration of potential energy surfaces, electronic structure information is generally lost. Particularly in the field of heterogeneous catalysis, simulated electron band structures provide fundamental insights into catalytic reactivity. This ab initio knowledge is preserved in semiempirical methods such as density functional tight binding (DFTB), which extend the accessible computational length and time scales beyond first-principles approaches. In this paper here we present Shell-Optimized Atomic Confinement (SOAC) DFTB electronic-part-only parametrizations for bulk and surface band structures of all d-block transition metals that enable efficient predictions of electronic descriptors for large structures or high-throughput studies on complex systems outside the computational reach of density functional theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

A Plasma Instability Theory of Gamma-Ray Burst Emission

A plasma instability theory is presented for the prompt radiation from gamma-ray bursts. In the theory, a highly relativistic shell interacts with the interstellar medium through the filamentation and the two-stream instabilities to convert bulk kinetic energy into electron thermal energy and magnetic field energy. The processes are not efficient enough to satisfy the Rankine-Hugoniot conditions, so a shock cannot form through this mechanism. Instead, the interstellar medium passes through the shell, with the electrons radiating during this passage. Gamma-rays are produced by synchrotron self-Compton emission. Prompt optical emission is also produced through this mechanism, while prompt radio emission is produced through synchrotron emission. The model timescales are consistent with the shortest burst timescales. To emit gamma-rays, the shell's bulk Lorentz factor must be $\simg 10(exp 3)$. For the radiative processes to be efficient, the interstellar medium density must satisfy a lower limit that is a function of the bulk Lorentz factor. Because the limits operate as selection effects, bursts that violate them constitute new classes. In particular, a class of optical and ultraviolet bursts with no gamma-ray emission should exist. The lower limit on the density of the interstellar medium is consistent with the requirements of the Compton attenuation theory, providing an explanation for why all burst spectra appear to be attenuated. Several tests of the theory are discussed, as are the next theoretical investigations that should be conducted.

Brainerd, Jerome J.↗
DOE OSTI2021

A measure of active interfaces in supported catalysts for high-temperature reactions

Formulating knowledge of structure-function relationships in heterogeneous catalysis is central to the design of efficient catalysts; yet, the elucidation of dominant reaction sites has remained as a challenge. Here, in this paper, we present a methodology that can be used to visualize metal-gas and metal-oxide-gas interfaces in three dimensions and to quantify their catalytic activity levels. As a case study, CH 4 oxidation occurring in a Pt/CeO 2 system is chosen. By employing thermally robust Pt@CeO 2 model catalysts with size-tunable and monodisperse cores, and gas-permeable shells, we reconstruct a series of structures in 3D via electron tomography and match the information to activity data and theoretical calculations. This strategy reveals that two different interfaces catalyze the CH 4 oxidation and that their contribution to the overall rate changes with the Pt size, temperature, and gas atmosphere. Our results provide an analytic platform on which to explore reaction pathways and mechanisms applicable to multiple reactions and materials.

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

Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO 2 Reduction

Catalysts promoting multielectron charge delocalization offer selectivity for the CO 2 reduction reaction (CO 2 RR) over the competing hydrogen evolution reaction. Here, we show metal–ligand exchange coupling as an example of charge delocalization that can determine the efficiency for photocatalytic CO 2 RR. A comparative evaluation of iron and cobalt complexes supported by the redox-active ligand tpyPY2Me establishes that the two-electron reduction of [Co(tpyPY2Me)] 2+ ([Co] 2+ ) occurs at potentials 770 mV more negative than the [Fe(tpyPY2Me)] 2+ ([Fe] 2+ ) analogue by maximizing the exchange coupling in the latter compound. The positive shift in the reduction potential promoted by metal–ligand exchange coupling drives [Fe] 2+ to be among the most active and selective molecular catalysts for photochemical CO 2 RR reported to date, maintaining up to 99% CO product selectivity with total turnover numbers (TONs) and initial turnover frequencies exceeding 30,000 and 900 min –1 , respectively. In contrast, [Co] 2+ shows much lower CO 2 RR activity, reaching only ca. 600 TON at 83% CO product selectivity under similar conditions accompanied by rapid catalyst decomposition. Further, the spin density plots of the two-electron reduced [Co] 0 complex implicate a paramagnetic open-shell doublet ground state compared to the diamagnetic open-shell singlet ground state of reduced [Fe] 0 , rationalizing the observed negative shift in two-electron reduction potentials from the [M] 2+ species and lowered CO 2 RR efficiency for the cobalt complex relative to its iron congener. This work emphasizes the contributions of multielectron metal–ligand exchange coupling in promoting effective CO 2 RR and provides a starting point for the broader incorporation of this strategy in catalyst design.

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

Thermal Stability of Au Rhombic Dodecahedral Nanocrystals Can Be Greatly Enhanced by Coating Their Surface with an Ultrathin Shell of Pt

Rhombic dodecahedral nanocrystals have been considered particularly difficult to synthesize because they are enclosed by {110}, a low-index facet with the greatest surface energy. Recently, we demonstrated the use of seed-mediated growth for the facile and robust synthesis of Au rhombic dodecahedral nanocrystals (AuRD). While the unique shape and surface structure of AuRD are desirable for potential applications in plasmonics and catalysis, respectively, their high surface energy makes them highly susceptible to thermal degradation. Here we demonstrate that it is feasible to greatly improve the thermal stability with some sacrifice to the plasmonic properties of the original AuRD by coating their surface with an ultrathin shell made of Pt. Our in situ electron microscopy analysis indicates that the ultrathin Pt coating can increase the thermal stability from 60 up to 450 °C, a trend that is also supported by the results from a computational study.

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

Dynamic Ligand Surface Chemistry of Excited PbS Quantum Dots

The ligand shell around colloidal quantum dots mediates the electron and energy transfer processes that underpin their use in optoelectronic and photocatalytic applications. In this work, we show that the surface chemistry of carboxylate anchoring groups of oleate ligands passivating PbS quantum dots undergoes significant changes when the quantum dots are excited to their excitonic states. Additionally, we directly probe the changes of surface chemistry using time-resolved mid-infrared spectroscopy that records the evolution of the vibrational frequencies of carboxylate groups following excitation of the electronic states. The data reveal a reduction of the Pb-O coordination of carboxylate anchoring groups to lead atoms at the quantum dot surfaces. The dynamic surface chemistry of the ligands may increase their surface mobility in the excited state and enhance the ability of molecular species to penetrate the ligand shell to undergo energy and charge transfer processes that depend sensitively on distance.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dynamic Evolution of Copper Nanowires during CO 2 Reduction Probed by Operando Electrochemical 4D-STEM and X-ray Spectroscopy

Nanowires have emerged as an important family of one-dimensional (1D) nanomaterials owing to their exceptional optical, electrical, and chemical properties. In particular, Cu nanowires (NWs) show promising applications in catalyzing the challenging electrochemical CO 2 reduction reaction (CO 2 RR) to valuable chemical fuels. Despite early reports showing morphological changes of Cu NWs after CO 2 RR processes, their structural evolution and the resulting exact nature of active Cu sites remain largely elusive, which calls for the development of multimodal operando time-resolved nm-scale methods. Here, in this study, we report that well-defined 1D copper nanowires, with a diameter of around 30 nm, have a metallic 5-fold twinned Cu core and around 4 nm Cu 2 O shell. Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) showed that as-synthesized Cu@Cu 2 O NWs experienced electroreduction of surface Cu 2 O to disordered (spongy) metallic Cu shell (Cu@Cu S NWs) under CO 2 RR relevant conditions. Cu@Cu S NWs further underwent a CO-driven Cu migration leading to a complete evolution to polycrystalline metallic Cu nanograins. Operando electrochemical four-dimensional (4D) STEM in liquid, assisted by machine learning, interrogates the complex structures of Cu nanograin boundaries. Correlative operando synchrotron-based high-energy-resolution X-ray absorption spectroscopy unambiguously probes the electroreduction of Cu@Cu 2 O to fully metallic Cu nanograins followed by partial reoxidation of surface Cu during postelectrolysis air exposure. This study shows that Cu nanowires evolve into completely different metallic Cu nanograin structures supporting the operando (operating) active sites for the CO 2 RR.

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

A new ejecta shell surrounding a Wolf-Rayet star in the LMC

We have obtained CCD spectra of newly discovered shell-like nebulae around the WN4 star Breysacher 13 and the WN1 star Breysacher 2 in the Large Magellanic Cloud (LMC). The shell around Br 13 shows definite signs of enrichment in both nitrogen and helium, having much stronger (N II) and He I emission lines than are seen in typical LMC H II regions. From the measured electron temperature of about 17,000 K in the shell, we derive He/H and N/O abundance ratios which are factors of 2 and more than 10 higher, respectively, than the average LMC interstellar values. The derived oxygen abundance in the Br 13 shell is down by a factor of 8 compared to the local LMC interstellar medium (ISM); however, the derived electron temperature is affected by the presence of an incomplete shock arising from the interaction of the stellar wind with photoionized material. This uncertainty does not affect the basic conclusion that the Br 13 shell is enriched by processed material from the Wolf-Rayet star. In contrast, the shell around Br 2 shows no clear evidence of enrichment. The nebular spectrum is characterized by extremely strong (O III) and He II emission and very weak (N II). We derive normal He, O, and N abundances from our spectrum. This object therefore appears to be simply a wind-blown structure associated with a relatively dense cloud near the Wolf-Rayet star, although the very high-ionization state of the gas is unusual for a nebula associated with a Wolf-Rayet star.

Garnett, Donald R.↗
NASA NTRS1991

The plasma environment of Uranus

An overview of the observational results on the plasma environment at Uranus is given, and the implications of these observations for magnetospheric physics at Uranus are discussed. During the Voyager 2 encounter with Uranus, an extended magnetosphere filled with a tenuous plasma was detected. This low-energy plasma was found to consist of protons and electrons, with no significant heavy ion contribution, and with a density in the regions sampled by the spacecraft of at most three electrons per cubic centimeter. The plasma electrons and ions exhibit both a thermal component (with temperatures of tens of eV) and a hot component (with temperatures of a few keV). The thermal ion component is observed both inside and outside an L-shell value near 5, whereas the hot ion and electron component is excluded from the region inside of that L-shell. The source of the thermal component of the plasma is either the planetary ionosphere or the neutral hydrogen corona surrounding Uranus, whereas the hot component is convected in from the magnetotail, with probably an ionospheric source.

Belcher, J. W.↗
DOE OSTI2022

Molecular-orbital-based machine learning for open-shell and multi-reference systems with kernel addition Gaussian process regression

We introduce a novel machine learning strategy, kernel addition Gaussian process regression (KA-GPR), in molecular-orbital-based machine learning (MOB-ML) to learn the total correlation energies of general electronic structure theories for closed- and open-shell systems by introducing a machine learning strategy. The learning efficiency of MOB-ML(KA-GPR) is the same as the original MOB-ML method for the smallest criegee molecule, which is a closed-shell molecule with multi-reference characters. In addition, the prediction accuracies of different small free radicals could reach the chemical accuracy of 1 kcal/mol by training on one example structure. Accurate potential energy surfaces for the H10 chain (closed-shell) and water OH bond dissociation (open-shell) could also be generated by MOB-ML(KA-GPR). To explore the breadth of chemical systems that KA-GPR can describe, we further apply MOB-ML to accurately predict the large benchmark datasets for closed- (QM9, QM7b-T, and GDB-13-T) and open-shell (QMSpin) molecules.

Chemistry↗
DOE OSTI2022

Huzinaga projection embedding for efficient and accurate energies of systems with localized spin-densities

We demonstrate the accuracy and efficiency of the restricted open-shell and unrestricted formulation of the absolutely localized Huzinaga projection operator embedding method. Restricted open-shell and unrestricted Huzinaga projection embedding in the full system basis is formally exact to restricted open-shell and unrestricted Kohn–Sham density functional theory, respectively. By utilizing the absolutely localized basis, we significantly improve the efficiency of the method while maintaining high accuracy. Furthermore, the absolutely localized basis allows for high accuracy open-shell wave function methods to be embedded into a closed-shell density functional theory environment. The open-shell embedding method is shown to calculate electronic energies of a variety of systems to within 1 kcal/mol accuracy of the full system wave function result. For certain highly localized reactions, such as spin transition energies on transition metals, we find that very few atoms are necessary to include in the wave function region in order to achieve the desired accuracy. This extension further broadens the applicability of our absolutely localized Huzinaga level-shift projection operator method to include open-shell species. Here, we apply our method to several representative examples, such as spin splitting energies, catalysis on transition metals, and radical reactions.

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

Broadband Frequency Conversion of Spectrally Incoherent Pulses and Initial Laser-Plasma Instabilities Mitigation Experiments

There is a need for efficient broadband frequency conversion schemes from the infrared, where optical pulses are efficiently amplified by solid-state laser materials, to the ultraviolet, a wavelength range more suitable for inertial confinement fusion (ICF). The current schemes are inadequate for broadband, spectrally incoherent optical pulses composed of a large number of frequency components distributed over a large frequency range. Implementing novel technologies that generate optical pulses with a large number of spectral components improves the laser-target interaction. In particular, it has long been believed that broad bandwidth mitigates the electron-plasma-wave instabilities that generate suprathermal electrons, which degrade ICF performance by increasing the fuel adiabat and reducing the shell areal density. It is important to develop a platform to demonstrate hot electron suppression caused by the larger available bandwidth, which has not previously been feasible in the laboratory. Experimentally measuring and theoretically assessing these effects with adequately benchmarked simulation codes are paramount to the design and development of novel laser facilities aiming at producing energy via laser fusion. The Laboratory for Laser Energetics is building a new laser facility, the Fourth-generation Laser for Ultrabroadband eXperiments (FLUX), to generate high-energy nanosecond laser pulses with fractional bandwidth larger than 1% in the ultraviolet and perform combined experiments with the 60-beam Omega facility. This large increase in bandwidth from the ~ 0.1% currently available on high-energy laser systems, is achieved by combining amplification in nonlinear optical parametric amplifiers (OPAs) around 1053 nm (1w) with nonlinear frequency conversion to the ultraviolet (around 351 nm, 3w). The novel scheme for frequency conversion is based on the noncollinear sum-frequency generation (SFG) of the angularly dispersed amplified 1w output with a narrowband 2w pulse, which is also used to pump the OPA system. The proposal funded scientific and engineering studies necessary to implement this novel laser facility, accelerated the SFG deployment by funding additional project team resources (shop time, engineers, and technicians), and funded preliminary experiments on the Omega Laser.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO 2 Reduction at Low Overpotentials

Biological and heterogeneous catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over the hydrogen evolution reaction (HER). Here, we report a molecular iron(II) system that captures this design concept in a homogeneous setting through the use of a redox non-innocent terpyridine-based pentapyridine ligand (tpyPY2Me). As a result of strong metal-ligand exchange coupling between the Fe(II) center and ligand, [Fe(tpyPY2Me)] 2+ exhibits redox behavior at potentials 640 mV more positive than the isostructural [Zn(tpyPY2Me)] 2+ analog containing the redox-inactive Zn(II) ion. This shift in redox potential is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand. The metal-ligand cooperativity in [Fe(tpyPY2Me)] 2+ drives the electrochemical reduction of CO 2 to CO at low overpotentials with high selectivity for CO 2 RR (>90%) and turnover frequencies of 100,000 s -1 with no degradation over 20 h. The decrease in the thermodynamic barrier engendered by this coupling also enables homogeneous CO 2 reduction catalysis in water without compromising selectivity or rates. Synthesis of the two-electron reduction product, [Fe(tpyPY2Me)] o , and characterization by X-ray crystallography, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), variable temperature NMR, and density functional theory (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a formal Fe(II) oxidation state with a doubly reduced ligand system. Furthermore, this work provides a starting point for the design of systems that exploit metal-ligand cooperativity for electrocatalysis where the electrochemical potential of redox non-innocent ligands can be tuned through secondary metal-dependent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗