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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Low ozone amounts during 1992 - 1993 from Nimbus 7 and Meteor 3 total ozone mapping spectrometers

The global distribution of ozone during the October 31, 1978, to May 6, 1993, observing lifetime of the Nimbus 7 total ozone mapping spectrometer (TOMS) is described, with emphasis on the low ozone amounts observed during 1992 and 1993. Ozone amount time series are extended beyong May 6, 1993, to the end of July 1993 using preliminary Meteor 3 TOMS data. Time series for zonally averaged ozone amounts show that there has not been a significant shift in the seasonal patterns of ozone maxima and minima caused by the Mount Pinatubo eruption or by the onset of very low ozone values during 1992 and 1993. There has been a relatively slow, nearly linear decrease in the amount of ozone over the entire globe from 1979 to the end of 1991, with rates ranging from no change at the equator to a 4 - 6% decrease per decade at midlatitudes and a 10 - 12% decrease per decade at higher latitudes. After the eruption of Mount Pinatubo during June 1991, the ozone amount decreased in the equatorial latitudes (10 deg S to 10 deg N) for about 6 months (-10 Dobson units (DU) between 0 deg and 10 deg S and -3 DU between 0 deg and 10 deg N). During 1992 and continuing into 1993, the rate of ozone decrease deviated from the previously linear trend with the onset of changes that were large in comparison with the historical range of ozone values from 1979 to 1991. The first of the large decreases in ozone amount occurred earlier, in February 1990 to May 1990, at 50 deg - 70 deg N. At high northern latitudes, the 1993 decreased ozone amounts were about 12.5% below the envelope of historical values; at midlatitudes they were about 7% lower; and at low latitudes they were about 4% lower. Area-weighted averages in the northern and southern hemispheres show that most of the 1992 - 1993 ozone losses have occurred in the northern hemisphere. The 1993 global average (70 deg S to 70 deg N) ozone amount is 3% below the 1979 to 1991 minimum, 5% below the historical envelope in the northern hemisphere, and near the lower boundary of the historical envelope in the southern hemisphere. In the 70 deg - 60 deg S latitude band, the ozone losses between 1979 and 1993 have reduced the annual minimum amount to values below those seen in the equatorial regions.

Herman, J. R.↗
NASA NTRS2004

Modeling of Sheath Ion-Molecule Reactions in Plasma Enhanced Chemical Vapor Deposition of Carbon Nanotubes

In many plasma simulations, ion-molecule reactions are modeled using ion energy independent reaction rate coefficients that are taken from low temperature selected-ion flow tube experiments. Only exothermic or nearly thermoneutral reactions are considered. This is appropriate for plasma applications such as high-density plasma sources in which sheaths are collisionless and ion temperatures 111 the bulk p!asma do not deviate significantly from the gas temperature. However, for applications at high pressure and large sheath voltages, this assumption does not hold as the sheaths are collisional and ions gain significant energy in the sheaths from Joule heating. Ion temperatures and thus reaction rates vary significantly across the discharge, and endothermic reactions become important in the sheaths. One such application is plasma enhanced chemical vapor deposition of carbon nanotubes in which dc discharges are struck at pressures between 1-20 Torr with applied voltages in the range of 500-700 V. The present work investigates The importance of the inclusion of ion energy dependent ion-molecule reaction rates and the role of collision induced dissociation in generating radicals from the feedstock used in carbon nanotube growth.

Hash, David B.↗
NASA NTRS2016

Predictive Simulation of Gas Adsorption in Fixed-Beds and Limitations due to the Ill-Posed Danckwerts Boundary Condition

The 1-D axially dispersed plug flow model is a mathematical model widely used for the simulation of adsorption processes. Lumped mass transfer coefficients such as the Glueckauf linear driving force (LDF) term and the axial dispersion coefficient are generally obtained by fitting simulation results to the experimental breakthrough test data. An approach is introduced where these parameters, along with the only free parameter in the energy balance equations, are individually fit to specific test data that isolates the appropriate physics. It is shown that with this approach this model provides excellent simulation results for the C02 on zeolite SA sorbent/sorbate system; however, for the H20 on zeolite SA system, non-physical deviations from constant pattern behavior occur when fitting dispersive experimental results with a large axial dispersion coefficient. A method has also been developed that determines a priori what values of the LDF and axial dispersion terms will result in non-physical simulation results for a specific sorbent/sorbate system when using the one-dimensional axially dispersed plug flow model. A relationship between the steepness of the adsorption equilibrium isotherm as indicated by the distribution factor, the magnitude of the axial dispersion and mass transfer coefficient, and the resulting non-physical behavior is derived. This relationship is intended to provide a guide for avoiding non-physical behavior by limiting the magnitude of the axial dispersion term on the basis of the mass transfer coefficient and distribution factor.

Knox, James Clinton↗
NASA NTRSDate not supplied

Constraints on triple oxygen isotope kinetics

The general assumption that systems are in equilibrium is convenient, but imperfect. Instead, the partial or full expression of kinetic reaction steps may need to be determined. Using an isotope fractionation Monte-Carlo model under the harmonic approximation (Figure 1 envelopes), we find the range of kinetic isotope effects (i.e., resulting from unidirectional chemical reactions) contains and exceeds the range of accessible equilibrium isotope effects. For the 16O-17O-18O system, accessible kinetic isotope effects can yield Δ′17O variations as large 0.8‰ from a single kinetic fractionation step. Reactions that yield the largest deviations from equilibrium are those with the largest molecular mass difference between decomposition fragments, typically the two products, such as a gas and solid generated from the thermal decomposition of an initial solid. For example, previously published experiments on the thermal decomposition of calcite (CaCO3) and dehydroxylation of brucite (Mg(OH)2) are matched by density functional theory models of each kinetic isotope effect, thus revealing their origin in mass-dependent reaction. Beyond oxygen, our approach applies to any system with more than two isotopes.

Oxygen isotopes↗
NASA NTRSDate not supplied

Constraints on Triple Oxygen Isotope Kinetics

Triple oxygen isotope methods (e.g., using δ 18 O, and Δ′ 17 O) have been used to classify meteorites, to constrain atmospheric chemistry, and to estimate primary productivity, among other uses. Such utility relies on the mass dependency of most chemical reactions: δ 17 O is proportional to δ 18 O by roughly a factor of 0.5. However, in detail, mass-dependency factors vary. While constraints on mass dependency are well established for equilibrium isotope effects, similar constraints for kinetic isotope effects are lacking. Using an ab initio Monte Carlo approach (see envelopes in Figure 1), we find the range of kinetic isotope effects (i.e., resulting from unidirectional chemical reactions) contains and exceeds the range of accessible equilibrium isotope effects for the 16 O 17 O 18 O system (Hayles and Killingsworth, 2022). Accessible kinetic isotope effects can yield Δ′ 17 O variations as large 0.8 ‰ from a single kinetic fractionation step. Reactions that yield the largest deviations from equilibrium are those with the largest molecular mass difference between decomposition fragments, typically the two products such as a gas and solid generated from the thermal decomposition of an initial solid. Comparison of DFT transition state model results against previously published experiments on the thermal decomposition of calcite (CaCO 3 ) (Miller et al., 2002) and dehydroxylation of brucite (Mg(OH) 2 ) (Clayton and Mayeda, 2009) show they are matched with mass-dependent kinetic isotope effects. This approach can be applied to any system with more than two isotopes.

Oxygen isotopes↗
NASA NTRS2019

Exploring the Utility of Machine Learning-Based Passive Microwave Brightness Temperature Data Assimilation over Terrestrial Snow in High Mountain Asia

This study explores the use of a support vector machine (SVM) as the observation operator within a passive microwave brightness temperature data assimilation framework (herein SVM-DA) to enhance the characterization of snow water equivalent (SWE) over High Mountain Asia (HMA). A series of synthetic twin experiments were conducted with the NASA Land Information System (LIS) at a number of locations across HMA. Overall, the SVM-DA framework is effective at improving SWE estimates (~70% reduction in RMSE relative to the Open Loop) for SWE depths less than 200 mm during dry snowpack conditions. The SVM-DA framework also improves SWE estimates in deep, wet snow (~45% reduction in RMSE) when snow liquid water is well estimated by the land surface model, but can lead to model degradation when snow liquid water estimates diverge from values used during SVM training. In particular, two key challenges of using the SVM-DA framework were observed over deep, wet snowpacks. First, variations in snow liquid water content dominate the brightness temperature spectral difference (TB) signal associated with emission from a wet snowpack, which can lead to abrupt changes in SWE during the analysis update. Second, the ensemble of SVM-based predictions can collapse (i.e., yield a near-zero standard deviation across the ensemble) when prior estimates of snow are outside the range of snow inputs used during the SVM training procedure. Such a scenario can lead to the presence of spurious error correlations between SWE and TB, and as a consequence, can result in degraded SWE estimates from the analysis update. These degraded analysis updates can be largely mitigated by applying rule-based approaches. For example, restricting the SWE update when the standard deviation of the predicted TB is greater than 0.05 K helps prevent the occurrence of filter divergence. Similarly, adding a thin layer (i.e., 5 mm) of SWE when the synthetic TB is larger than 5 K can improve SVM-DA performance in the presence of a precipitation dry bias. The study demonstrates that a carefully constructed SVM-DA framework cognizant of the inherent limitations of passive microwave-based SWE estimation holds promise for snow mass data assimilation.

Kwon, Yonghwan↗
DOE OSTI2022

Constraints on the CKM angle γ from B ± → Dh ± decays using D → h ± h' ∓ π 0 final states

A data sample collected with the LHCb detector corresponding to an integrated luminosity of 9 fb –1 is used to measure eleven CP violation observables in B ± → Dh ± decays, where h is either a kaon or a pion. The neutral D meson decay is reconstructed in the three-body final states: K ± π ∓ π o ; π + π – π o ; K + K – π o and the suppressed π ± K ∓ π o combination. The mode where a large CP asymmetry is expected, B ± → [π ± K ∓ π o ] D K ± , is observed with a significance greater than seven standard deviations. The ratio of the partial width of this mode relative to that of the favoured mode, B ± → [K ± π ∓ π o ] D K ± , is R ADS(K) = (1.27 ± 0.16 ± 0.02) × 10 –2 . Evidence for a large CP asymmetry is also seen: A ADS(K) = –0.38 ± 0.12 ± 0.02. Constraints on the CKM angle γ are calculated from the eleven reported observables.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1992

Charge collection at large angles of incidence

Charge collection exhibited by p-n junctions, which have at least one small dimension, deviates from the geometric assumptions commonly used in SEU (single event upset) testing. The amount of charge collected did not increase with the secant of the angle of incidence. The number of events under the peak in the charge collection spectrum did not decrease as the cosine of the angle of incidence. Both the position of the peak and the number of events under the peak measured at a given angle of incidence depended upon which symmetry axis of the device was chosen to be the axis of rotation.

Mcnulty, P. J.↗
NASA NTRS2019

Prior biosphere model impact on global terrestrial CO2 fluxes estimated from OCO-2 retrievals

This study assesses the impact of different state of the art global biospheric CO2 flux models, when applied as prior information, on inverse model “top-down” estimates of terrestrial CO2 fluxes obtained when assimilating Orbiting Carbon Observatory 2 (OCO-2) observations. This is done with a series of observing system simulation experiments (OSSEs) using synthetic CO2 column-average dry air mole fraction (XCO2) retrievals sampled at the OCO-2 satellite spatiotemporal frequency. The OSSEs utilized a 4-D variational (4D-Var) assimilation system with the GEOS-Chem global chemical transport model (CTM) to estimate CO2 net ecosystem exchange (NEE) fluxes using synthetic OCO-2 observations. The impact of biosphere models in inverse model estimates of NEE is quantified by conducting OSSEs using the NASA-CASA, CASA-GFED, SiB-4, and LPJ models as prior estimates and using NEE from the multi-model ensemble mean of the Multiscale Synthesis and Terrestrial Model Intercomparison Project as the “truth”. Results show that the assimilation of simulated XCO2 retrievals at OCO-2 observing modes over land results in posterior NEE estimates which generally reproduce “true” NEE globally and over terrestrial TransCom-3 regions that are well-sampled. However, we find larger spread among posterior NEE estimates, when using different prior NEE fluxes, in regions and seasons that have limited OCO-2 observational coverage and a large range in “bottom-up” NEE fluxes. Seasonally averaged posterior NEE estimates had standard deviations (SD) of ∼10 % to ∼50 % of the multi-model-mean NEE for different TransCom-3 land regions with significant NEE fluxes (regions/seasons with a NEE flux ≥0.5 PgC/yr). On a global average, the seasonally averaged residual impact of the prior model NEE assumption on the posterior NEE spread is ∼10 %–20 % of the posterior NEE mean. Additional OCO-2 OSSE simulations demonstrate that posterior NEE estimates are also sensitive to the assumed prior NEE flux uncertainty statistics, with spread in posterior NEE estimates similar to those when using variable prior model NEE fluxes. In fact, the sensitivity of posterior NEE estimates to prior error statistics was larger than prior flux values in some regions/times in the tropics and Southern Hemisphere where sufficient OCO-2 data were available and large differences between the prior and truth were evident. Overall, even with the availability of spatiotemporally dense OCO-2 data, noticeable residual differences (up to ∼20 %–30 % globally and 50 % regionally) in posterior NEE flux estimates remain that were caused by the choice of prior model flux values and the specification of prior flux uncertainties.

Sajeev Philip↗
DOE OSTI2026

Lattice Relaxations in Bixbyite‐Structured Rare‐Earth Sesquioxides

This report examines atomic relaxations in rare‐earth sesquioxides with the cubic bixbyite crystal structure. In particular, the experimentally determined unit cell atom positions in bixbyite compounds are compared to “ideal” bixbyite atom positions, where the concept of ideality is based on similarities between the bixbyite and fluorite crystal structures. Analyses indicate that all rare‐earth sesquioxide compounds deviate from ideality in similar ways and that there is a trend wherein the magnitudes of these atomic deviations decrease with increasing cationic size. The deviations from an ideal, fluorite‐like structure produce highly distorted coordination polyhedra and variations in metal‐oxygen bond lengths. A modified bond valence sum analysis revealed that the first nearest neighbor cation‐anion bond length variations lead to large (20%) variations in cation‐anion bond strength. This report also provides a qualitative analysis regarding the accuracy of atomic relaxed deviation parameters, based on x‐ray diffraction measurements. The analysis indicates that uncertainties in the accuracy of measured oxygen relaxed deviation parameters in bixbyite sesquioxides are likely much greater than the published uncertainties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Numerical modeling of chemical looping oxidative dehydrogenation of ethane in parallel packed beds

Chemical looping oxidative dehydrogenation (CL-ODH) of ethane has the potential to be a highly efficient alternative to steam cracking for ethylene production. Accurate reactor modeling is of critical importance to efficiently scale up and optimize this new technology. This study reports a one-dimensional, heterogeneous packed bed model to simulate the CL-ODH of ethane to ethylene with a Na 2 MoO 4 -promoted CaTi 0.1 Mn 0.9 O 3 redox catalyst. Here, the overall reaction kinetics was well-described by coupling the gas-phase steam cracking of ethane with the reduction kinetics of the redox catalyst by H 2 and C 2 H 4 . The impact of H 2 on the formation rate of CO 2 byproduct from C 2 H 4 conversion was also thoroughly investigated to validate the applicability of the kinetic model under operational environments. The temperature variation within the different CL-ODH steps and the temperature distribution along the bed were also carefully considered. The accuracy of the model was validated by experiments conducted in a large lab-scale packed bed reactor (200 g catalyst loading), with an average deviation of 2.8% in terms of ethane conversion and ethylene yield. The model was subsequently used to optimize the operating parameters of the CL-ODH reactor, indicating that up to 63.7% single-pass C 2 +olefin yield can be achieved with the current redox catalyst bed whereas further optimization of the redox catalyst to inhibit C 2 H 4 activation can result in 69.4% single-pass C 2 +yield while maintaining low CO 2 selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Edge dislocation mediated anomalous charge transfer in face centered cubic high entropy alloys

The charge transfer in alloys dictates their structural and functional properties. The presence of the line defect can influence the charge transfer characteristics in alloys. The edge dislocation-volume misfit interaction in high entropy alloys is a critical area of interest concerning the development of accurate solid solution strengthening models for these materials. The evolution of the volume misfit of atoms is either studied empirically using Vegard's law or mechanistically using \emph{ab initio} calculations, without considering the effect of edge dislocation on charge transfer explicitly. In this work, we show the influence of edge dislocation on the charge transfer in CoCrFeMnNi, CoCrNi and CoNi using large-scale \emph{ab initio} calculations. The anomalous charge transfer characteristics, in terms of deviations from electronegativity trends, are demonstrated, which are dictated by electronegativity equalisation rather than pair-atom interactions. The deviation of atomic volume in the compressive and tensile stress regions of the edge dislocation is rationalised in terms of anomalous magneto-volume fluctuations in such alloys.

Ghosh, Swarnava [ORNL] (ORCID:0000000338005264)↗
DOE OSTI2024

Non-thermal emission in gap-mode plasmon photoluminescence

Abstract Photoluminescence from spatially inhomogeneous plasmonic nanostructures exhibits fascinating wavelength-dependent nonlinear behaviors due to the intraband recombination of hot electrons excited into the conduction band of the metal. The properties of the excited carrier distribution and the role of localized plasmonic modes are subjects of debate. In this work, we use plasmonic gap-mode resonators with precise nanometer-scale confinement to show that the nonlinear photoluminescence behavior can become dominated by non-thermal contributions produced by the excited carrier population that strongly deviates from the Fermi-Dirac distribution due to the confinement-induced large-momentum free carrier absorption beyond the dipole approximation. These findings open new pathways for controllable light conversion using nonequilibrium electron states at the nanoscale.

Science & Technology - Other Topics↗
DOE OSTI2023

Fast uncertainty estimates in deep learning interatomic potentials

Deep learning has emerged as a promising paradigm to give access to highly accurate predictions of molecular and material properties. A common short-coming shared by current approaches, however, is that neural networks only give point estimates of their predictions and do not come with predictive uncertainties associated with these estimates. Existing uncertainty quantification efforts have primarily leveraged the standard deviation of predictions across an ensemble of independently trained neural networks. This incurs a large computational overhead in both training and prediction, resulting in order-of-magnitude more expensive predictions. Here, we propose a method to estimate the predictive uncertainty based on a single neural network without the need for an ensemble. This allows us to obtain uncertainty estimates with virtually no additional computational overhead over standard training and inference. We demonstrate that the quality of the uncertainty estimates matches those obtained from deep ensembles. We further examine the uncertainty estimates of our methods and deep ensembles across the configuration space of our test system and compare the uncertainties to the potential energy surface. Finally, we study the efficacy of the method in an active learning setting and find the results to match an ensemble-based strategy at order-of-magnitude reduced computational cost.

Chemistry↗
NASA NTRS1983

Oceanographic and meteorological research based on the data products of SEASAT

De-aliased SEASAT SASS vector winds obtained during the GOASEX (Gulf of Alaska SEASAT Experiment) program were processed to obtain superobservations centered on a one degree by one degree grid. The results provide values for the combined effects of mesoscale variability and communication noise on the individual SASS winds. Each grid point of the synoptic field provides the mean synoptic east-west and north-south wind components plus estimates of the standard deviations of these means. These superobservations winds are then processed further to obtain synoptic scale vector winds stress fiels, the horizontal divergence of the wind, the curl of the wind stress and the vertical velocity at 200 m above the sea surface, each with appropriate standard deviations for each grid point value. The resulting fields appear to be consistant over large distances and to agree with, for example, geostationary cloud images obtained concurrently. Their quality is far superior to that of analyses based on conventional data.

Pierson, W. J.↗
NASA NTRS1984

High-frequency wave normals in the solar wind

High-frequency (0.01-0.04 Hz) magnetic fluctuations in 506 ten-minute intervals of contemporaneous Explorer 35 and Apollo 12 measurements made in the solar wind near the morning side of the earth's bow shock show the presence of a large population of disturbances resembling Alfven waves. Each wavefront normal is systematically aligned (median deviation = 35 deg) with the associated ten-minute average of the magnetic field. Because of variability in the direction of this ten-minute average, from one interval to another, the coupled wavefront-normal distribution is nearly isotropic in solar ecliptic coordinates, in contrast with the results of other studies of waves at much lower frequency indicating outward propagation from the sun. Presumably the high frequency waves discussed here are stirred into isotropy (in solar ecliptic coordinates) by following the low frequency fluctuations. As these waves maintain their alignment of wavefront-normal with the field ten-minute average despite the great variation of the field ten-minute average, a strong physical alignment constraint is inferred.

Herbert, F.↗
NASA NTRS1990

Accretion disk emission from a BL Lacertae object

The accretion disk is an attractive model for BL Lac objects because of its preferred axis and high efficiency. While the smooth continuum spectra of BL Lacs do not show large UV bumps, in marked contrast to quasars, high quality simultaneous data do reveal deviations from smoothness. Using detailed calculations of cool accretion disk spectra, the best measured ultraviolet and soft x ray spectra of the BL Lac object PKS 2155-304 are fitted. The mass and accretion rate required are determined. A hot disk or corona could comptonize soft photons from the cool disk and produce the observed power law spectrum in the 1 to 10 keV range. The dynamic time scales in the disk regions that contribute most of the observed ultraviolet and soft x ray photons are consistent with the respective time scales for intensity variations. The mass derived from fitting the continuum spectrum is consistent with the limit derived from the fastest hard x ray variability.

Urry, C. Megan↗
NASA NTRS1994

Observational tests for nonequilibrium ionization in the solar corona

Nonequilibrium ionization may be produced by a variety of processes in the solar corona, for example, by mass flows through the large temperature gradients of the transition region or by impulsive heating and cooling. Any deviation from equilibrium ionization would have a strong effect on the radiation from the corona and on the interpretation of solar observations; hence, it is important to determine observational signatures of nonequilibrium. The temperature-sensitive line ratios can be used as such signatures. We examine the line ratios: C IV I(1548.2 A)/I(312.4 A), O IV I(789.4 A)/I(554.4 A), O V I(629.7 A)/I(172.2 A), O VI I(1031.9 A)/I(173.0 A) and O VI I(1031.9 A)/I(150.1 A). These line ratios are calculated for four coronal loop models that have a steady flow and that are known to have significant departures from equilibrium ionization. Our results indicate that, in general, nonequilibrium causes a considerable reduction in the line ratios, more than an order of magnitude in the downflowing leg of the loop model with the largest mass flows. We find that the C IV line ratio is the most sensitive to nonequilibrium. We discuss the implications of our results for observations, specifically, the observations expected from the upcoming SOHO mission.

Spadaro, D.↗