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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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34 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Clarifying the quantum mechanical origin of the covalent chemical bond

Lowering of the electron kinetic energy (KE) upon initial encounter of radical fragments has long been cited as the primary origin of the covalent chemical bond based on Ruedenberg’s pioneering analysis of H$^{+}_{2}$ and H 2 and presumed generalization to other bonds. This work reports KE changes during the initial encounter corresponding to bond formation for a range of different bonds; the results demand a re-evaluation of the role of the KE. Bonds between heavier elements, such as H 3 C–CH 3 , F–F, H 3 C–OH, H 3 C–SiH 3 , and F–SiF 3 behave in the opposite way to H$^{+}_{2}$ and H 2 , with KE often increasing on bringing radical fragments together (though the total energy change is substantially stabilizing). The origin of this difference is Pauli repulsion between the electrons forming the bond and core electrons. These results highlight the fundamental role of constructive quantum interference (or resonance) as the origin of chemical bonding. Differences between the interfering states distinguish one type of bond from another.

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

Energetics and kinetics of various cyano radical hydrogen abstractions

The cyano radical (CN) is an abundant, open-shell molecule found in a variety of environments, including the atmosphere, the interstellar medium and combustion processes. In these environments, it often reacts with small, closed-shell molecules via hydrogen abstraction. Both carbon and nitrogen atoms of the cyano radical are reactive sites, however the carbon is more reactive with reaction barrier heights generally between 2–15 kcal mol -1 lower than those of the analogous nitrogen. The CN + HX → HCN/HNC + X, with X = H, CH 3 , NH 2 , OH, F, SiH 3 , PH 2 , SH, Cl, C 2 H, CN reactions have been studied at a high-level of theory, including CCSD(T)-F12a. Finally, kinetics were obtained over the 100–1000 K temperature range, showing excellent agreement with those rate constants that have been determined experimentally.

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

Catalytic reduction of carbon dioxide by a zinc hydride compound, [Tptm]ZnH, and conversion to the methanol level

The zinc hydride compound, [Tptm]ZnH, may achieve the reduction of CO 2 by (RO) 3 SiH (R = Me, Et) to the methanol oxidation level, (MeO) x Si(OR) 4–x , via the formate species, HCO 2 Si(OR) 3 . Furthermore, because insertion of CO 2 into the Zn–H bond is more facile than insertion of HCO 2 Si(OR) 3 , conversion of HCO 2 Si(OR) 3 to the methanol level only occurs to a significant extent in the absence of CO 2 .

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

Ultraviolet H 2 luminescence in molecular clouds induced by cosmic rays

Context. Galactic cosmic rays (CRs) play a crucial role in ionisation, dissociation, and excitation processes within dense cloud regions where UV radiation is absorbed by dust grains and gas species. CRs regulate the abundance of ions and radicals, leading to the formation of more and more complex molecular species, and determine the charge distribution on dust grains. A quantitative analysis of these effects is essential for understanding the dynamical and chemical evolution of star-forming regions. Aims. The CR-induced photon flux has a significant impact on the evolution of the dense molecular medium in its gas and dust components. This study evaluates the flux of UV photons generated by CRs to calculate the photon-induced dissociation and ionisation rates of a vast number of atomic and molecular species, as well as the integrated UV photon flux. Methods. To achieve these goals, we took advantage of recent developments in the determination of the spectra of secondary electrons, in the calculation of state-resolved excitation cross sections of H 2 by electron impact, and of photodissociation and photoionisation cross sections. Results. We calculated the H 2 level population of each rovibrational level of the X, B, C, B′, D, B″, D′, and a states. We then computed the UV photon spectrum of H 2 in its line and continuum components between 72 and 700 nm, with unprecedented accuracy, as a function of the CR spectrum incident on a molecular cloud, the H 2 column density, the isomeric H 2 composition, and the dust properties. The resulting photodissociation and photoionisation rates are, on average, lower than previous determinations by a factor of about 2, with deviations of up to a factor of 5 for the photodissociation of species such as AlH, C 2 H 2 , C 2 H 3 , C 3 H 3 , LiH, N 2 , NaCl, NaH, O 2 + , S2, SiH, l-C 4 , and l-C 5 H. A special focus is given to the photoionisation rates of H 2 , HF, and N 2 , as well as to the photodissociation of H 2 , which we find to be orders of magnitude higher than previous estimates. We give parameterisations for both the photorates and the integrated UV photon flux as a function of the CR ionisation rate, which implicitly depends on the H 2 column density, as well as the dust properties.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Scaling of silicon nanoparticle growth in low temperature flowing plasmas

Low temperature plasmas are an emerging method to synthesize high quality nanoparticles (NPs). An established and successful technique to produce NPs is using a capacitively coupled plasma (CCP) in cylindrical geometry. Although a robust synthesis technique, optimizing or specifying NP properties using CCPs, is challenging. In this paper, results from a computational investigation for the growth of silicon NPs in flowing inductively coupled plasmas (ICPs) using Ar/SiH 4 gas mixtures of up to a few Torr are discussed. ICPs produce more locally constrained and quiescent plasma potentials. These positive plasma potentials produce an electrostatic trap for negatively charged NPs, which can significantly extend the residence time of NPs in the plasma, which in turn provides a controllable period for particle growth. The computational platforms used in this study consist of a two-dimensional plasma hydrodynamics model, a three-dimensional nanoparticle growth and trajectory tracking model, and a molecular dynamics simulation for deriving reactive sticking coefficients of silane radicals on Si NPs. Trends for the nanoparticle growth as a function of SiH 4 inlet fraction, gas residence time, energy deposition per particle, pressure, and reactor diameter are discussed. The general path for particle synthesis is the trapping of small NPs in the positive electrostatic potential, followed by entrainment in the gas flow upon reaching a critical particle size. Optimizing or controlling NP synthesis then depends on the spatial distribution of plasma potential, the density of growth species, and the relative time that particles spend in the electrostatic trap and flowing through higher densities of growth species upon leaving the trap.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Impact of heavy quark and quarkonium data on nuclear gluon PDFs

A clear understanding of nuclear parton distribution functions (nPDFs) plays a crucial role in the interpretation of collider data taken at the Relativistic Heavy Ion Collider, the Large Hadron Collider (LHC), and in the near future at the Electron-Ion Collider. Even with the recent inclusions of vector boson and light meson production data, the uncertainty of the gluon PDF remains substantial and limits the interpretation of heavy ion collision data. To obtain new constraints on the nuclear gluon PDF, we extend our recent nCTEQ15WZ+SIH analysis to inclusive quarkonium and open heavy-flavor meson production data from the LHC. This vast new data set covers a wide kinematic range and puts strong constraints on the nuclear gluon PDF down to x ≲ 10 -5 . The theoretical predictions for these data sets are obtained from a data-driven approach, where proton-proton data are used to determine effective scattering matrix elements. This approach is validated with detailed comparisons to existing next-to-leading order calculations in nonrelativistic QCD for quarkonia and in the general-mass variable-flavor-number scheme for the open heavy-flavored mesons. In addition, the uncertainties from the data-driven approach are determined using the Hessian method and accounted for in the PDF fits. This extension of our previous analyses represents an important step toward the next generation of PDFs not only by including new data sets, but also by exploring new methods for future analyses.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Hydrosilyation of CO 2 using a silatrane hydride: structural characterization of a silyl formate compound

The silatrane hydride compound, [N(CH 2 CH 2 O) 3 ]SiH, reacts with CO 2 in the presence of the [tris(2-pyridylthio)methyl]zinc hydride complex, [Tptm]ZnH, to afford the silyl formate and methoxide derivatives, [N(CH 2 CH 2 O) 3 ]SiO 2 CH and [N(CH 2 CH 2 O) 3 ]SiOCH 3 . The molecular structure of [N(CH 2 CH 2 O) 3 ]SiO 2 CH has been determined by X-ray diffraction, thereby demonstrating that the formate ligand adopts a distal conformation in which the uncoordinated oxygen atom resides with a trans-like disposition relative to silicon. In conclusion, density functional theory calculations indicate that the atrane motif of [N(CH 2 CH 2 O) 3 ]SiO 2 CH is flexible, such that the energy of the molecule changes relatively little as the Si···N distance varies over the range 2.0–3.0 Å.

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

Ultraviolet H 2 luminescence in molecular clouds induced by cosmic rays

Context. Galactic cosmic rays (CRs) play a crucial role in ionisation, dissociation, and excitation processes within dense cloud regions where UV radiation is absorbed by dust grains and gas species. CRs regulate the abundance of ions and radicals, leading to the formation of more and more complex molecular species, and determine the charge distribution on dust grains. A quantitative analysis of these effects is essential for understanding the dynamical and chemical evolution of star-forming regions. Aims. The CR-induced photon flux has a significant impact on the evolution of the dense molecular medium in its gas and dust components. This study evaluates the flux of UV photons generated by CRs to calculate the photon-induced dissociation and ionisation rates of a vast number of atomic and molecular species, as well as the integrated UV photon flux. Methods. To achieve these goals, we took advantage of recent developments in the determination of the spectra of secondary electrons, in the calculation of state-resolved excitation cross sections of H 2 by electron impact, and of photodissociation and photoionisation cross sections. Results. We calculated the H 2 level population of each rovibrational level of the X, B, C, B', D, B", D', and a states. We then computed the UV photon spectrum of H 2 in its line and continuum components between 72 and 700 nm, with unprecedented accuracy, as a function of the CR spectrum incident on a molecular cloud, the H 2 column density, the isomeric H 2 composition, and the dust properties. The resulting photodissociation and photoionisation rates are, on average, lower than previous determinations by a factor of about 2, with deviations of up to a factor of 5 for the photodissociation of species such as AlH, C 2 H 2 , C 2 H 3 , C 3 H 3 , LiH, N 2 , NaCl, NaH, O$^+_2$, S 2 , SiH, l-C 4 , and l-C 5 H. A special focus is given to the photoionisation rates of H 2 , HF, and N 2 , as well as to the photodissociation of H 2 , which we find to be orders of magnitude higher than previous estimates. We give parameterisations for both the photorates and the integrated UV photon flux as a function of the CR ionisation rate, which implicitly depends on the H 2 column density, as well as the dust properties.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

The APOGEE Data Release 16 Spectral Line List

The updated H-band spectral-line list (from λ15000–17000) adopted by the Apache Point Observatory Galactic Evolution Experiment (APOGEE) for the SDSS-IV Data Release 16 (DR16) is presented in this work. The APOGEE line list is a combination of atomic and molecular lines, with data drawn from laboratory, theoretical, and astrophysical sources. Oscillator strengths and damping constants are adjusted using high signal-to-noise, high-resolution spectra of the Sun, and α Boo (Arcturus), as “standard stars.” Updates to the DR16 line list, as compared to the previous DR14 version, include the addition of molecular H{sub 2}O and FeH lines, as well as a much larger (by a factor of ∼4) atomic line list, including a significantly greater number of transitions with hyperfine splitting. More recent references and line lists for the crucial molecules, CO and OH, as well as for C{sub 2} and SiH, are also included. In contrast to DR14, DR16 contains measurable lines from the heavy neutron-capture elements cerium (as Ce ii), neodymium (as Nd ii), and ytterbium (as Yb ii), as well as one line from rubidium (as Rb i), which may be detectable in a small fraction of APOGEE red giants.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Flammable Gas Generation and Control at the Idaho Completion Project Legacy Combustible Gas Generation - 20191

On April 11, 2018, four drums containing transuranic waste at the Idaho National Laboratory underwent over-pressurization, ejecting their lids and spreading radiological waste within a facility. An investigation has found that waste in the drums generated methane gas, which contributed to the event. Subsequent to the investigation, the potential for drums to have methane and other flammable analytes whose concentrations could approach or exceed the lower flammability limit (LFL) and the adequacy of the controls to prevent or mitigate a possible deflagration was evaluated. An extensive review of the historical records was performed to determine how many drums exceed the LFL. The historical record identified a small quantity of drums that exceeded the LFL for xylene, hydrogen, and methane. The primary codified applicable code or standard for handling drums is 29 CFR 1910.120 (j) 'Handling Drums and Containers.' It is used throughout the commercial and government sector. This code is integrated throughout the Fluor Idaho safety management programs and procedures to control the Standard Industrial Hazards (SIHs) associated with drum and container handling. Example requirements include: - Drums and containers are inspected, and their integrity assured prior to being moved. - Site operations are organized to minimize the amount of drum or container movement. - When there is a reasonable possibility of flammable atmospheres being present, material handling equipment and hand tools are of the type to prevent sources of ignition. Drums and containers under pressure, as evidenced by bulging or swelling, are not moved until the cause for excess pressure is determined and appropriate containment procedures have been implemented to protect employees from explosive relief of the drum. Drums which exceed the WIPP FGA limit have NCRs associated with them. Once a drum fails flammable gas sampling, an NCR is initiated. The NCR drives placement into NCR dense pack rows. A standing order drives placement of the FGA failures to a single planer segregation location. These drums are not allowed for further processing or shipment until the NCR has been cleared. Once in the single planer rows, follow-up FGA testing is performed by CCP. The NCR is dispositioned by follow-up sampling occurring after adequate time has been provided for the gas to diffuse through the filter assembly, or, in some cases, the drums are repackaged into additional drums to reduce the source term. To date, the ICP project has performed approximately 1.5 million drums moves without a deflagration event due to combustible gas generation. Flammable gas generation in a transuranic waste drum is not unique to the ICP but is common across the DOE complex. Based on the experience at Idaho, application of industry standards is sufficient to control the risk of drum deflagration due to drum movements. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Measurement of optically-pumped electron spin polarization in n-GaAs at high external electric fields

We use the technique of time-resolved Kerr rotation (TRKR) to measure the electron spin polarization generated by optical spin pumping in an n-type gallium arsenide (GaAs) epilayer when an external electric field is simultaneously applied on the sample. The drift of the electron spins under the influence of the external electric field is captured with spatial scans of the pump–probe separation. A significant decay in the magnitude of electron spin polarization with electric field is observed and is attributed to the increased inhomogeneous broadening caused by the field-induced drift and the hot electron effects. Here, we extend the electric field range to as high as the Gunn threshold field in the measurement and we do not observe a spin amplification effect due to the spin Gunn effect under our experimental scheme.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Gunn threshold voltage characterization in GaAs devices with wedge-shaped tapering

Here, we fabricate gallium arsenide-based devices with a wedge-shaped tapering region connected to a rectangular-shaped region and measure the threshold voltage required to trigger the Gunn effect. The threshold voltage reduction is attributed to the focusing of the electric field toward the narrower end of the device and is effective when the device has a steep enough tapering. We also model the electric field profile for the tapered devices using an intuitive graphical approach and the finite element method and provide estimates for the threshold voltages of tapered devices. Finally, we compare the estimates to the measured values and provide possible reasons for the discrepancies. We believe the capability of threshold voltage reduction with the wedge-shaped tapering design could be useful in device applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Illumination-induced modulation of conductivity and Gunn oscillation properties in epitaxial GaAs

In this work, we illuminate a gallium arsenide (GaAs) Gunn device and study the light-induced changes of Gunn oscillation properties. We observe that illumination leads to the modulation of the Gunn threshold voltage, the Gunn oscillation magnitude, and the coherency of Gunn oscillation, with the nature of the modulation being closely related to the position of illumination on the device. These effects are attributed to the generation of optically excited carriers, which results in the modulation of conductivity and the electric field profile along the device. The finite element method is used to simulate the change of the field profile of the Gunn device caused by illumination. We also report an unexpected phenomenon of Gunn oscillation property manipulation with an optical chopper. In addition, wavelength-dependent, power-dependent, and pulsed illumination measurements are performed to help with further understanding the observations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Electrical control of spin relaxation anisotropy during drift transport in a two-dimensional electron gas

Spin relaxation was studied in a two-dimensional electron gas confined in a wide GaAs quantum well. Recently, the control of the spin relaxation anisotropy by diffusive motion was first shown in D. Iizasa et al., arXiv:2006.08253. Here, we demonstrate electrical control by drift transport in a system with two subbands occupied. The combined effect of in-plane and gate voltages was investigated using time-resolved Kerr rotation. Furthermore, the measured relaxation time presents strong anisotropy with respect to the transport direction. For an in-plane accelerating electric field along [110], the lifetime was strongly suppressed irrespective of the applied gate voltage. Remarkably, for transport along [$1\bara{1}0$], the data shows spin lifetime that was gate dependent and longer than in the [110] direction regardless of the in-plane voltage. In agreement, independent results of anisotropic spin precession frequencies are also presented. Nevertheless, the long spin lifetime, strong anisotropy and drift response seen in the data are beyond the existing models for spin drift and diffusion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Spatially-resolved measurements of spin valley polarization in MOCVD-grown monolayer WSe 2

Time-resolved Kerr rotation microscopy is used to generate and measure spin valley polarization in MOCVD-grown monolayer tungsten diselenide (WSe 2 ). The Kerr signal reveals bi-exponential decay with time constants of 100 ps and 3 ns. Measurements are performed on several triangular flakes from the same growth cycle and reveal larger spin valley polarization near the edges of the flakes. This spatial dependence is observed across multiple WSe 2 flakes in the Kerr rotation measurements but not in the spatially resolved reflectivity or microphotoluminescence data. Time-resolved pump-probe overlap measurements further reveal that the Kerr signal’s spatial dependence is not due to spin diffusion on the nanosecond timescale.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Electron Spin Polarization in Large Electric Fields

This project investigated the effects of large electric fields on electron spin polarization in semiconductors, which is of interest for spin-based electronics (“spintronics”) and quantum information processing. It has been theoretically proposed that large electric fields could potentially preserve or amplify electron spin polarization, which would make it easier to generate, transport, and detect spin polarization in spin-based devices; however, previous measurements had not measured the response of electron spin polarization at large electric fields. During this project, methods to perform measurements of electron spin polarization at large electric fields were developed and performed using ultrafast time- and spatially-resolved magneto-optical spectroscopy, high-voltage pulses, and lock-in detection. The device geometry was engineered to reduce the threshold voltage required to reach the Gunn threshold, and the effect of optical illumination on the sample conductivity and Gunn oscillations was investigated. Electron spin polarization measurements were performed at electric fields up to and beyond the Gunn threshold for the device. The measurements showed that the electron spin polarization magnitude decreased with increasing electric field in the devices measured, and a spin amplification effect was not observed. However, these effects could potentially exist in a different material or in a material with a different doping concentration or in a different device geometry.

36 MATERIALS SCIENCE↗