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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
NASA NTRS1977

A survey of interstellar molecular hydrogen. I

Data from the Copernicus satellite's ultraviolet telescope were used to survey column densities of atomic and molecular hydrogen from a large sample of early-type stars; these data have bearing on an eventual understanding of diffuse and dense interstellar clouds. Column densities are derived by fitting damping profiles to the observed spectra, most of which exhibit strong damping lines in the lower rotational levels surveyed. Plots of dust column density, fractional abundance of molecular hydrogen, and the logarithm of fractional abundance versus total gas column density are given for many of the stars; stars with abnormally large or small hydrogen column densities, as well as some distant stars at high galactic latitudes, are considered. Equilibrium and nonequilibrium theories accounting for the abundance of interstellar hydrogen are compared, and support is found in the data for an account which balances hydrogen formation on interstellar grains with destruction through photodissociation. Overall averages for atomic and molecular hydrogen levels in the galactic plane are also calculated.

Savage, B. D.↗
NASA NTRS1983

Photochemistry of N2(+) in the daytime F region

The photochemistry of N2(+) in the daytime F region continues to be a source of concern due primarily to the uncertain roles of the metastable O+(2D) ion and possible vibrational excitation. This investigation adopts a unique subset of data from the Atmospheric Explorer C satellite that spans distinct regions near the low-latitude F peak wherein either chemical reactions or electron processes alternatively control the N2(+) abundances. Concentrations of N2(+) calculated according to current theory and including recent laboratory data for O+(2D) losses via N2 are found to exceed ionospheric observations between 220 and 400 km by a factor near 2. Relevant characteristics of the basic molecular ion concentration measurements are described, along with an analysis for select orbits conducted according to current photochemical equilibrium theory. Possible simple modifications of this theory are discussed in terms of the constraints suggested by the nature of the observations.

Breig, E. L.↗
NASA NTRS1986

Ultraviolet spectrometer observations of Uranus

The Voyager 2 UV spectrometer was used to scan the Uranus atmosphere at wavelengths from 500-1700 A with a field of view of 0.1 x 0.86 deg. The temperature and composition of the upper atmosphere were determined through occultations of light from gamma Pegasi, nu Geminorum and the sun. The data indicated a substantial gas density (100 million H atoms/cu cm) at about 28,000 km from the Uranus center, suggesting that gas drag plays a significant role in ring evolution. The distributions of CH4 and C2H2 in the lower atmosphere were also estimated. An electroglow emission was detected on the sunlit side, and attributed to emissions from atomic and molecular hydrogen excited by low energy electrons. An auroral glow was also observed, and exhibited evidence of an energy input equal to that of the electroglow. Finally, estimates of the C2H2 mixing ratio and the vertical column abundance of H2 are calculated.

Broadfoot, A. L.↗
NASA NTRS1986

Molecular ions in the circumstellar envelope of IRC + 10216

Assuming a steady and spherically symmetric mass loss, the spatial distribution of the ionization in a C-rich circumstellar envelope (CSE) is calculated, and it is shown that molecular ions dominate the ionization and chemistry of a large part of the CSE. Cosmic ray ionization of molecular hydrogen yields H3(+), and the photoionization of acetylene and neutral carbon yields C2H2(+) and C(+). In the system, the primary ions generate a series of heavier molecular ions by reactions with neutral molecules before being destroyed by dissociative recombination. The most promising candidate for mm-wavelength detection is found to be HCO(+), and IRC + 10216 antenna temperatures are calculated for different telescope sizes. Photoproduced C2H2(+), the most abundant intermediate distance CSE ion, may be responsible for the synthesis of various heavy hydrocarbon molecules at levels observed in IRC + 10216.

Glassgold, A. E.↗
NASA NTRS1989

The carbon budget in the outer solar nebula

The compositional contrast between the giant-planet satellites and the significantly rockier Pluto/Charon system is indicative of different formation mechanisms; cosmic abundance calculations, in conjunction with an assumption of the Pluto/Charon system's direct formation from solar nebula condensates, strongly suggest that most of the carbon in the outer solar nebula was in CO form, in keeping with both the inheritance from the dense molecular clouds in the interstellar medium, and/or the Lewis and Prinn (1980) kinetic-inhibition model of solar nebula chemistry. Laboratory studies of carbonaceous chondrites and Comet Halley flyby studies suggest that condensed organic material, rather than elemental carbon, is the most likely candidate for the small percentage of the carbon-bearing solid in the outer solar nebula.

Simonelli, Damon P.↗
NASA NTRS1995

Stable isotope analysis at the molecular level: A new approach for determining the origins of amino acids in the Murchison meteorite

A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta C-13 values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in C-13 relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta C-13 values (+5 to +30 per mill, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary resutls are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.

Engel, M. H.↗
NASA NTRS1993

Eddy mixing coefficient upper limit derived from the photochemical balance of O2

This work is based on the study of the photochemical balance of molecular oxygen in the martian atmosphere by using a one-dimensional model of photochemical reactions involving species derived from CO2 and H2O. The model is basically similar to one used previously for the study of the regulation of CO on a global scale, but the chemical rates are taken from another source. In the present scheme, the regulation of molecular oxygen is studied over timescales of the order of its photochemical lifetime (approximately equals 30 yr), which is much shorter than typical escape timescales. Thus, the escape fluxes are fixed to the values given by 3 and 4. We examine the calculated equilibrium abundances of O2 for given thermal, eddy diffusion coefficients and H2O profiles. The thermal profile is taken from in the lower atmosphere. At higher levels, in order to include the diurnal and seasonal thermal profile variability, we have also used the IRTM data. In order to study the influence of both temperature and pressure profiles on the O2 mixing ratio, we have made several tests corresponding to different martian seasons. The results show that the influence of pressure and temperature is quantitatively weak compared to the one of K and of the water vapor density (H2O). Thus, in the following we have fixed the pressure at the surface to a value of 7 mbar and we have used unique standard thermal profile corresponding to a profile roughly averaged over the year, the season, and the day: T equal 205 K at 0 km altitude, 175 K at 25 km, and 145 K at 50 km.

Rosenqvist, J.↗
NASA NTRS1975

Uranian methane abundance, rotational temperature, and effective pressure from the 6800 A band

Measurements of the methane absorption features at 6800 A in two spectrograms of Uranus have been analyzed on the working hypothesis that the features are the R branch of the 5 mu(3) rotation-vibration overtone. Internal and external consistencies in temperature calculations from the measurements give increased confidence that the band identification and rotational-quantum-number assignments to band members are correct. Parametric fitting of synthetic reflecting-layer and homogeneous scattering-layer spectra to the spectrograms is attempted. The best-fit methane abundances, taken with recent estimates of the molecular hydrogen abundance, correspond to an average C:H ratio between 1.5 and 25 times larger than the solar ratio. Even greater enrichment of the C:H ratio may occur below the visible cloud boundary. High spectroscopic resolution of the present data permits direct measurement of the methane line halfwidth in Uranus's spectrum. The halfwidth corresponds to an effective pressure greater than 3 atm, depending on the mixture of atmospheric gases. Pressure in this range, at the methane rotational temperature of between 93 and 100 K, is inconsistent with current Uranus atmosphere models having solar elemental-abundance ratios. It is consistent with models which are considerably enriched in 'heavier' constituents.

Bergstralh, J. T.↗
NASA NTRS2005

Experimental Study on Interactions Between H Atoms and Organic Haze

In Titan s atmosphere composed of N2 and CH4, irradiations of both solar ultraviolet light and charged particles induce active chemical reactions. In the processes of these reactions, a large amount of hydrogen (H) atoms are expected to be formed by dissociation of CH4 and other hydrocarbons [e.g., 1, 2]. Theoretical models suggest that these active H atoms need to be converted to stable hydrogen molecules (H2) efficiently to maintain unsaturated hydrocarbons and organic haze in Titan s atmosphere [e.g., 1]. Furthermore, molecular hydrogen is an important greenhouse effect gas in Titan s atmosphere, and small variation in its abundance strongly affects Titan s surface temperature [3]. Thus, the formation of H2 molecules from H atoms is a key reaction for both the atmospheric chemistry and the surface environment of Titan. Although several numerical calculations have been conducted to investigate the atmospheric chemistry of Titan with hypothesized recombination reactions of H atoms, such as catalytic scheme of C4H2 [e.g., 1, 2], it is still unclear what chemical reaction is responsible for the conversion of H atoms to H2 molecules in Titan s atmosphere.

Sekine, Y.↗
DOE OSTI2025

Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts

The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd 8 Au 92 nanoparticles supported on silica using surface-sensitive techniques, we report that whether Pd overgrowth occurs before or after Au nanoparticle deposition onto the support controls the surface Pd ensemble size and abundance. These differences in Pd ensembles influence catalytic reactivity in H 2 –D 2 isotope exchange and benzaldehyde hydrogenation, which, in correlation with theoretical calculations, is used to elucidate the active site(s) in each reaction. To clarify how the synthetic sequence controls the formation of Pd ensembles, we combine numerical wetting calculations and molecular dynamics simulations (with a machine-learned force field) to visualize Pd deposition and migration on the nanoparticle surface, respectively. Our results suggest that the nanoparticle–support interface restricts nanoparticle accessibility to Pd deposition, which consequently controls the Pd ensemble size, illustrating the critical role of nanoscale wetting phenomena during bimetallic catalyst preparation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Examining normal modes as fundamental heat carriers in amorphous solids: The case of amorphous silicon

Normal mode decomposition of atomic vibrations has been used to provide microscopic understanding of thermal transport in amorphous solids for decades. In normal mode methods, it is naturally assumed that atoms vibrate around their equilibrium positions, and that individual normal modes are the fundamental vibrational excitations transporting heat. With the abundance of predictions from normal mode methods and experimental measurements now available, we carefully analyze these calculations in amorphous silicon, a model amorphous solid. We find a number of discrepancies, suggesting that treating individual normal modes as fundamental heat carriers may not be accurate in amorphous solids. Furthermore, our classical and ab initio molecular dynamics simulations of amorphous silicon demonstrate a large degree of atomic diffusion, especially at high temperatures, leading to the conclusion that thermal transport in amorphous solids could be better described starting from the perspectives of liquid physics rather than from crystalline solids.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Creating Frustrated Lewis Pairs in Defective Boron Carbon Nitride for Electrocatalytic Nitrogen Reduction to Ammonia

Abstract The electrocatalytic nitrogen reduction reaction (NRR) on metal‐free catalysts is an attractive alternative to the industrial Haber–Bosch process. However, the state‐of‐the‐art metal‐free electrocatalysts still suffer from low Faraday efficiencies and low ammonia yields. Herein, we present a molecular design strategy to develop a defective boron carbon nitride (BCN) catalyst with the abundant unsaturated B and N atoms as Lewis acid and base sites, which upgrades the catalyst from a single “Lewis acid catalysis” to “frustrated Lewis pairs (FLPs) catalysis.” 14 N 2 / 15 N 2 exchange experiments and density functional theory (DFT) calculations reveal that FLPs can adsorb an N 2 molecule to form a six‐membered ring intermediate, which enables the cleavage of N 2 via a pull–pull effect, thereby significantly reducing the energy barrier to −0.28 eV. Impressively, BCN achieves a high Faraday efficiency of 18.9 %, an ammonia yield of 20.9 μg h −1 mg −1 cat. , and long‐term durability.

Lin, Wenwen↗
DOE OSTI2022

Creating Frustrated Lewis Pairs in Defective Boron Carbon Nitride for Electrocatalytic Nitrogen Reduction to Ammonia

Abstract The electrocatalytic nitrogen reduction reaction (NRR) on metal‐free catalysts is an attractive alternative to the industrial Haber–Bosch process. However, the state‐of‐the‐art metal‐free electrocatalysts still suffer from low Faraday efficiencies and low ammonia yields. Herein, we present a molecular design strategy to develop a defective boron carbon nitride (BCN) catalyst with the abundant unsaturated B and N atoms as Lewis acid and base sites, which upgrades the catalyst from a single “Lewis acid catalysis” to “frustrated Lewis pairs (FLPs) catalysis.” 14 N 2 / 15 N 2 exchange experiments and density functional theory (DFT) calculations reveal that FLPs can adsorb an N 2 molecule to form a six‐membered ring intermediate, which enables the cleavage of N 2 via a pull–pull effect, thereby significantly reducing the energy barrier to −0.28 eV. Impressively, BCN achieves a high Faraday efficiency of 18.9 %, an ammonia yield of 20.9 μg h −1 mg −1 cat. , and long‐term durability.

Lin, Wenwen↗
NASA NTRS1986

The microwave and far-infrared spectra of the O-(18)H radical

Far-infrared laser magnetic resonance (LMR) spectroscopy was used to calculate the frequencies, wavelengths, and line strengths for transitions of O-(18)H molecules at microwave and far-infrared frequencies. In this experiment, a molecular transition frequency is tuned into coincidence with that of a fixed frequency laser by the application of a variable magnetic field. The O-(18)H radicals, detected in natural abundance (0.20 percent), were produced by the reaction of hydrogen atoms with nitrogen dioxide. These data together with microwave frequencies ascertained by Gottlieb, Redford, and Smith (1974) were used to determine the parameters of an effective Hamiltonian. Rotational levels up to J = 5.5 were involved. Results are indicated schematically and the low-lying energy levels of O-(18)H are shown. It is concluded that the frequencies of transitions between levels studied directly in the LMR experiment are reliable.

Comben, E. R.↗
DOE OSTI2026

Investigating trends in actinide covalency and magnetism with 35/37 Cl SSNMR spectroscopy and first-principles calculations

Solid-state NMR (SSNMR) spectroscopy is a powerful technique for studying actinide chemistry but has been significantly limited due to the complex paramagnetism, and radiological hazards presented by these materials. Lanthanide and actinide salts often feature magnetic ordering and can be paramagnetic, ferromagnetic, or antiferromagnetic depending on temperature and electronic structure. Paramagnetic interactions can manifest in SSNMR both as secular spectral shifts and/or couplings as well as contributions from non-secular relaxation. Both effects can be directly measured with NMR and used to extrapolate rich chemical information such as coordination environments, bonding characteristics, local molecular dynamics, and correlation times. Typically, these studies are carried out on high-γ and highly abundant NMR-active isotopes (e.g., 1 H, 6/7 Li, 19 F, 23 Na, etc.) or on enriched rare isotopes (e.g., 2 H and 17 O), which can be expensive. Herein, we present a facile methodology to measure the 35/37 Cl electric-field gradient (EFG) and paramagnetic shift anisotropy (SA) tensor components using static wideline SSNMR measurements of LaCl 3 , NdCl 3 , UCl 3 , and UCl 4 . The static powder spectra were measured with both 35 Cl and 37 Cl SSNMR to increase the fidelity of the extracted tensor parameters. Variable temperature NMR of a select case confirms the Curie–Weiss paramagnetism. Relaxation measurements of both nuclei further corroborate observations owing to the paramagnetic relaxation enhancement and reveal simultaneous quadrupolar relaxation mechanisms. Density functional theory (DFT) calculations using Hubbard U corrections to the uranium valence orbitals show excellent agreement with experimental EFG tensor parameters and help describe the bonding characteristics in these lanthanide and actinide systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1979

An ab initio investigation of the structure, vibrational frequencies, and intensities of HO2 and HOCl

The infrared spectral intensities for HOCl and HO2 have been calculated using a new ab initio technique. Theoretical results for the geometries, vibrational frequencies, and the dipole moments of these species are also reported. All of the calculations were performed at the SCF level using near Hartree-Fock quality basis sets. The results for the molecular geometries and the vibrational frequencies are in good agreement with available experimental data. It is believed that the computed intensities are accurate to at least 50%. The results should be helpful in attempts to determine the stratospheric abundance of HOCl and HO2 by in situ infrared spectroscopic measurements.

Komornicki, A.↗
NASA NTRS1986

C3H2 observations as a diagnostic probe for molecular clouds

Recently the three-membered ring molecule, cyclopropenylidene, C3H2, has been identified in the laboratory and detected in molecular clouds by Thaddeus, Vrtilek and Gottlieb (1985). This molecule is wide-spread throughout the Galaxy and has been detected in 25 separate sources including cold dust clouds, circumstellar envelopes, HII regions, and the spiral arms observed against the Cas supernova remnant. In order to evaluate the potential of C3H2 as a diagnostic probe for molecular clouds, and to attempt to identify the most useful transitions, statistical equilibrium calculations were carried out for the lowest 24 levels of the ortho species and the lowest 10 levels of the para species. Many of the sources observed by Matthews and Irvine (1985) show evidence of being optically thick in the 1(10)-1(01) line. Consequently, the effects of radiative trapping should be incorporated into the equilibrium calculations. This was done using the Large Velocity Gradient approximation for a spherical cloud of uniform density. Some results of the calculations for T(K)=10K are given. Figures are presented which show contours of the logarithm of the ratio of peak line brightness temperatures for ortho-para pairs of lines at similar frequencies. It appears that the widespread nature of C3H2, the relatively large strength of its spectral lines, and their sensitivity to density and molecular abundance combine to make this a useful molecule for probing physical conditions in molecular clouds. The 1(10)-1(01) and 2(20)-2(11) K-band lines may be especially useful in this regard because of the ease with which they are observed and their unusual density-dependent emission/absorption properties.

Avery, L. W.↗
NASA NTRS1996

The Abundances of Charged Particles in Protostellar Cores

We investigate the abundances of charged particles in very dense (10(exp 5) cm(exp -3) approx. less than n(sub H2) approx less than 10(exp 14) cm(exp -3) molecular cloud (protostellar) cores. We focus on the dust grains, which are the dominant charge carriers for high densities. Previous studies have investigated the abundances of charged grains in the case that the grain radii follow an MRN distribution. We account for the transfer of charge between grains of different size, an effect that was ignored in previous calculations, but which is significant in determining the total abundance of charged grains. The consequences for star formation are considered.

Desch, Steven J.↗