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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Identification of dislocation-related and point-defects in III-As layers for silicon photonics applications

Abstract The aim of this paper is to identify, analyze and compare the defects present in III-As, as a function of dislocation density, and as a function of the presence/absence of quantum dots (QDs). Such materials are of fundamental importance for the development of lasers and photodiodes for silicon photonics. The study is based on an extensive deep-level transient spectroscopy investigation, carried out on GaAs pin diodes grown on Si and on GaAs (that differ in the dislocation density), with and without embedded QDs. The original results described in this paper demonstrate that: (a) we were able to identify four different defects within the device grown on Si (three electron and one hole traps) and one defect (hole trap) in the device on GaAs, common to both samples; (b) all the majority carrier traps identified are located near midgap, i.e. are efficient non-radiative recombination centers; (c) such defects are absent (or non-detectable) in the sample grown on GaAs substrate, having a very low dislocation density; (d) the presence of QDs does not result in additional defects within the semiconductor material; (e) the analysis of the capture kinetics revealed that two of the identified traps are related to point defects, whereas the other two traps can be associated with point defects located near a dislocation; (f) a comparison with previous reports indicate that the detected traps are related to native III-As defects, or to oxygen-related complexes.

Physics↗
NASA NTRS1972

Study of optical properties of X-ray sources

A series of optical and X-ray observations of Sco X-1 and Cyg X-2 by UHURU satellite is reported. Results for Sco X-1 show a definite correlation between optical and X-ray intensity and thus indicate a common emitting region with the source being quiet and having no short term fluctuations bigger than 10%. Spectra reveal the presence of a high excitation complex at wavelength 4650 due to N III-C III. Spectra of a faint 15-mag red object NW of the radio position indicate that Cyg X-1 is associated with a bright B supergiant star. The flux from the edges of the Cygnus Loop in the coronal line at wavelength 5303 was measured to be less than five times ten to the minus nine power erg/sq cm/sterad/sec (0.017 R) in a 3-A band centered on the line. This indicates substantial broadening of the line profile by mass motion or that the temperature is somewhat higher than the present estimate from X-ray data.

Vandenbout, P. A.↗
NASA NTRS1983

Analysis of the visible spectra of concentrated chromic chloride solutions

In the development of the Redox Energy Storage System, the electrical storage efficiency is low due to the complex chemical reaction of the chromium II and III species. Several studies dealing with the processes occurring at the catalyzed carbon electrode during the charging and discharging of the system are described.

Bunch, W. D.↗
NASA NTRS2019

Large Male Anthropomorphic Test Device (ATD) Finite Element Model (FEM) Correlation Improvement

As part of an activity for the Commercial Crew Program (CCP), a NASA Engineering and Safety Center (NESC) team conducted tests of small female, medium male, and large male Hybrid III anthropomorphic test device (ATD) head-neck complexes. The results were compared to simulation results from ATD finite element model (FEM) predictions to determine the validity and fidelity of ATD models for use in certifying CCP vehicles. The NESC was requested to help improve the large male ATD FEM to better represent physical responses. This report contains the outcome of the NESC assessment.

Kelly, Michael J.↗
DOE OSTI2025

Triel-Defined Helicity in One-Dimensional III–VI–VII van der Waals Crystals

Inorganic extended lattice solids that bear complex helical motifs manifest unusual physical and quantum states that arise due to their noncentrosymmetric or chiral nature. However, the systematic understanding of how elemental composition influences the structure and physical properties in helical inorganic crystals has been precluded by the rarity of these materials and the lack of modular phases that display such motifs. Here, we report the synthesis of AlSeI single crystals, the first aluminum-containing helical crystal in the III-VI-VII 1D van der Waals class. AlSeI completes the experimentally accessible triel series in the helical selene iodides alongside InSeI and GaSeI. Using the Al, Ga, and In triel series in this selene iodide class, we experimentally demonstrate the evolution of the local quasi-tetrahedral building unit geometry, chain packing, helical parameters, and band gaps based primarily on the identity of the triel atom. Our results underscore the chemical modularity of these phases, the broad range of helical parameters, and the spectrum of electronic states from the visible to the ultraviolet range in this emergent class of 1D, exfoliable, and helical extended lattice solids.

Chemical structure↗
DOE OSTI2019

Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer

Concepts for the thermodynamically challenging synthesis of weak N–H bonds by photoinduced proton coupled electron transfer are explored. Upon irradiation with blue light, ammonia synthesis was achieved from the manganese nitride ( tBu Salen)MnN ( tBu Salen = ( S,S )-(+)- N,N' -bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) in the presence of 9,10-dihydroacridine and a ruthenium photocatalyst in i PrOH solution. Although in one case the ruthenium complex bears a remote N–H bond that weakens to 41 kcal mol –1 upon irradiation, control experiments with the N -methylated analog demonstrate the ruthenium complex serves as a photoreductant rather than hydrogen-atom transfer catalyst in aprotic solvents. Luminescence quenching experiments support a ruthenium(II)/(III) cycle rather than a ruthenium(I)/(II) alternative. Identification of the manganese complex following ammonia synthesis was also accomplished.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States

Pentavalent actinyl nitrate complexes An V O 2 (NO 3 ) 2 - were produced by elimination of two NO 2 from An III (NO 3 ) 4 - for An = Pu, Am, Cm, Bk, and Cf. Density functional theory (B3LYP) and relativistic multireference (CASPT2) calculations confirmed the AnO 2 (NO 3 ) 2 - as AnVO 2 + actinyl moieties coordinated by nitrates. Computations of alternative An III O 2 (NO 3 ) 2 - and AnI V O 2 (NO 3 ) 2 - revealed significantly higher energies. Previous computations for bare AnO 2 + indicated AnVO 2 + for An = Pu, Am, Cf, and Bk, but Cm III O 2 + : electron donation from nitrate ligands has here stabilized the first Cm V complex, Cm V O 2 (NO 3 ) 2 - . Structural parameters and bonding analyses indicate increasing An-NO 3 bond covalency from Pu to Cf, in accordance with principles for actinide separations. Atomic ionization energies effectively predict relative stabilities of oxidation states; more reliable energies are needed for the actinides.

36 MATERIALS SCIENCE↗
NASA NTRS2023

The 17 April 2021 Widespread Solar Energetic Particle Event

A complex and long-lasting solar eruption on 17 April 2021 produced a widespread solar energetic particle (SEP) event that was observed by five longitudinally well-separated observers in the inner heliosphere that covered distances to the Sun from 0.42 to 1 au: BepiColombo, Parker Solar Probe, Solar Orbiter, STEREO A, and near-Earth spacecraft. The event was the second widespread SEP event detected in solar cycle 25, and it produced relativistic electrons and protons. It was associated with a long-lasting solar hard X-ray flare that showed multiple hard X-ray peaks over a duration of one hour. The event was further accompanied by a medium-fast coronal mass ejection (CME) with a speed of 880 km s -1 that drove a shock, an extreme ultraviolet wave, and long-lasting and complex radio burst activity that showed four distinct type III burst groups over a period of 40 min. We aim to understand the reason for the wide spread of elevated SEP intensities in the inner heliosphere as well as identify the underlying source regions of the observed energetic electrons and protons. We applied a comprehensive multi-spacecraft analysis of remote-sensing observations and in situ measurements of the energetic particles and interplanetary context to attribute the SEP observations at the different locations to the various potential source regions at the Sun. We used an ENLIL simulation to characterize the complex interplanetary state and its role in the energetic particle transport. The magnetic connection between each spacecraft and the Sun was determined using ballistic backmapping in combination with potential field source surface extrapolations in the lower corona. Using also a reconstruction of the coronal shock front, we then determined the times when the shock establishes magnetic connections with the different observers. Radio observations were used to characterize the directivity of the four main injection episodes, which were then employed in a 2D SEP transport simulation to test the importance of these different injection episodes. A comprehensive timing analysis of the inferred solar injection times of the SEPs observed at each spacecraft suggests different source processes being important for the electron and proton events. Comparison among the characteristics and timing of the potential particle sources, such as the CME-driven shock or the flare, suggests a stronger shock contribution for the proton event and a more likely flare-related source for the electron event. In contrast to earlier studies on widespread SEP events, we find that in this event an important ingredient for the wide SEP spread was the wide longitudinal range of about 110 o covered by distinct SEP injections, which is also supported by our SEP transport modeling.

sun↗
DOE OSTI2015

A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment

Herein we describe facial and meridional isomers of [Rh III (pyalk) 3 ], as well as meridional [Rh IV (pyalk) 3 ] + {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible Rh III/IV redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV–visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Emergence of californium as the second transitional element in the actinide series

Abstract A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5 f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 OSTI2023

Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis -Dioxo Fleeting Intermediate

The activation of chalcogen–chalcogen bonds using organometallic uranium complexes has been well documented for S–S, Se–Se, and Te–Te bonds. In stark contrast, reports concerning the ability of a uranium complex to activate the O–O bond of an organic peroxide are exceedingly rare. Herein, we describe the peroxide O–O bond cleavage of 9,10-diphenylanthracene-9,10-endoperoxide in nonaqueous media, mediated by a uranium(III) precursor [(( Me,Ad ArO) 3 N)U III (dme)] to generate a stable uranium(V) bis-alkoxide complex, namely, [(( Me,Ad ArO) 3 N)U V (DPAP)]. This reaction proceeds via an isolable, alkoxide-bridged diuranium(IV/IV) species, implying that the oxidative addition occurs in two sequential, single-electron oxidations of the metal center, including rebound of a terminal oxygen radical. Furthermore, this uranium(V) bis-alkoxide can then be reduced with KC 8 to form a uranium(IV) complex, which upon exposure to UV light, in solution, releases 9,10-diphenylanthracene to generate a cyclic uranyl trimer through formal two-electron photooxidation. Analysis of the mechanism of this photochemical oxidation via density functional theory (DFT) calculations indicates that the formation of this uranyl trimer occurs through a fleeting uranium cis-dioxo intermediate. At room temperature, this cis-configured dioxo species rapidly isomerizes to a more stable trans configuration through the release of one of the alkoxide ligands from the complex, which then goes on to form the isolated uranyl trimer complex.

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

Artificial Iron Proteins: Modeling the Active Sites in Non-Heme Dioxygenases

An important class of non-heme dioxygenases contains a conserved Fe binding site that consists of a 2-His-1-carboxylate facial triad. Results from structural biology show that, in the resting state, these proteins are six-coordinate with aqua ligands occupying the remaining three coordination sites. Here, we have utilized biotin–streptavidin (Sav) technology to design new artificial Fe proteins (ArMs) that have many of the same structural features found within active sites of these non-heme dioxygenases. An Sav variant was isolated that contains the S 112 E mutation, which installed a carboxylate side chain in the appropriate position to bind to a synthetic Fe II complex confined within Sav. Structural studies using X-ray diffraction (XRD) methods revealed a facial triad binding site that is composed of two N donors from the biotinylated ligand and the monodentate coordination of the carboxylate from S 112 E. Two aqua ligands complete the primary coordination sphere of the Fe II center with both involved in hydrogen bond networks within Sav. The corresponding Fe III protein was also prepared and structurally characterized to show a six-coordinate complex with two exogenous acetato ligands. The Fe III protein was further shown to bind an exogenous azido ligand through replacement of one acetato ligand. Spectroscopic studies of the ArMs in solution support the results found by XRD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

TPSAS-NF1676L-33512-DND

INTRODUCTION: In an effort to quantify the predictive capability of the Livermore Software Technology Corporation (LSTC)-provided Hybrid III (small female, mid-size male, and large male) anthropomorphic test device (ATD) finite element models (FEMs) within aerospace loading environments, the National Aeronautics and Space Administration (NASA) performed a series of sled tests with the isolated head-neck complex of each ATD. These tests and subsequent modeling efforts revealed significant deficiencies in the large male head neck FEM. Differences in both the shape and material properties between the FEM and the physical ATD were identified. In order to improve the predictive response of the FEM, a model development effort was undertaken to update the head-neck complex to better represent the geometric and material properties of the physical ATD.METHODS: To better match the physical geometry, a new neck component model was meshed and implemented into the Hybrid III large male head-neck complex. The updated geometry and weight were verified against measurements of the physical ATD to insure accuracy. The primary source of material discrepancy between the physical ATD and FEM was found to be in the material definition of the rubber neck pucks. Using LS-Opt the material properties of this part were calibrated to match physical response of the head-neck complex in the isolated head-neck testing performed. RESULTS AND DISCUSSION: The updated geometry and calibrated material properties were shown to significantly improve the FEM predictive accuracy under lateral, rear, and frontal impacts with combined horizontal and vertical loading. The results of this study demonstrate an effective means for improving ATD FEM response through isolated component level testing and material parameter optimization. The improved and quantified accuracy of the Hybrid III large male FEM head-neck complex stemming from with work lends to confidence in its future use for occupant protection evaluation of large male occupants

J Putnam↗
DOE OSTI2019

Snapshots of a Migrating H‐Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring‐Protonated Iron(I) Isomer

Abstract We report the characterization of an S = iron π‐complex, [Fe(η 6 ‐IndH)(depe)] + (Ind=Indenide (C 9 H 7 − ), depe=1,2‐bis(diethylphosphino)ethane), which results via C−H elimination from a transient Fe III hydride, [Fe(η 3 :η 2 ‐Ind)(depe)H] + . Owing to weak M−H/C−H bonds, these species appear to undergo proton‐coupled electron transfer (PCET) to release H 2 through bimolecular recombination. Mechanistic information, gained from stoichiometric as well as computational studies, reveal the open‐shell π‐arene complex to have a BDFE C‐H value of ≈50 kcal mol −1 , roughly equal to the BDFE Fe‐H of its Fe III −H precursor (Δ G °≈0 between them). Markedly, this reactivity differs from related Fe(η 5 ‐Cp/Cp*) compounds, for which terminal Fe III −H cations are isolable and have been structurally characterized, highlighting the effect of a benzannulated ring (indene). Overall, this study provides a structural, thermochemical, and mechanistic foundation for the characterization of indenide/indene PCET precursors and outlines a valuable approach for the differentiation of a ring‐ versus a metal‐bound H‐atom by way of continuous‐wave (CW) and pulse EPR (HYSCORE) spectroscopic measurements.

Drover, Marcus W.↗
DOE OSTI2019

Snapshots of a Migrating H‐Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring‐Protonated Iron(I) Isomer

Abstract We report the characterization of an S = iron π‐complex, [Fe(η 6 ‐IndH)(depe)] + (Ind=Indenide (C 9 H 7 − ), depe=1,2‐bis(diethylphosphino)ethane), which results via C−H elimination from a transient Fe III hydride, [Fe(η 3 :η 2 ‐Ind)(depe)H] + . Owing to weak M−H/C−H bonds, these species appear to undergo proton‐coupled electron transfer (PCET) to release H 2 through bimolecular recombination. Mechanistic information, gained from stoichiometric as well as computational studies, reveal the open‐shell π‐arene complex to have a BDFE C‐H value of ≈50 kcal mol −1 , roughly equal to the BDFE Fe‐H of its Fe III −H precursor (Δ G °≈0 between them). Markedly, this reactivity differs from related Fe(η 5 ‐Cp/Cp*) compounds, for which terminal Fe III −H cations are isolable and have been structurally characterized, highlighting the effect of a benzannulated ring (indene). Overall, this study provides a structural, thermochemical, and mechanistic foundation for the characterization of indenide/indene PCET precursors and outlines a valuable approach for the differentiation of a ring‐ versus a metal‐bound H‐atom by way of continuous‐wave (CW) and pulse EPR (HYSCORE) spectroscopic measurements.

Drover, Marcus W.↗