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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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NASA NTRS2005

Accretion Flows in Magnetic White Dwarf Systems

We received Type A and B funding under the NASA Astrophysics Data Program for the analysis and interpretation of hard x-ray data obtained by the Rossi X-ray Timing Explorer and other NASA sponsored missions for Intermediate Polars (IPS) and Polars. For some targets, optical data was available. We reduced and analyzed the X-ray spectra and the X-ray and optical (obtained at the Cerro Tololo Inter-American Observatory) timing data using detailed shock models (which we constructed) to place constraints on the properties of the accreting white dwarfs, the high energy emission mechanisms of white dwarfs, and the large-scale accretion flows of Polars and IPS. IPS and Polars are white dwarf mass-transfer binaries, members of the larger class of cata,clysmic variables. They differ from the bulk of the cataclysmic variables in that they contain strongly magnetic white dwarfs; the white dwarfs in Polars have B, = 7 to 230 MG and those in IPS have B, less than 10 MG. The IPS and Polars are both examples of funneled accretion flows in strong magnetic field systems. The IPS are similar to x-ray pulsars in that accretion disks form in the systems which are disrupted by the strong stellar magnetic fields of the white dwarfs near the stellar surface from where the plasma is funneled to the surface of the white dwarf. The localized hot spots formed at the footpoints of the funnels coupled with the rotation of the white dwarf leads to coherent pulsed x-ray emission. The Polars offer an example of a different accretion topology; the magnetic field of the white dwarf controls the accretion flow from near the inner Lagrangian point of the system directly to the stellar surface. Accretion disks do not form. The strong magnetic coupling generally leads to synchronous orbital/rotational motion in the Polars. The physical system in this sense resembles the Io/Jupiter system. In both IPS and Polars, pulsed emission from the infrared to x-rays is produced as the funneled flows merge onto the white dwarfs through the formation of strong radiating shock waves. A comparative study of the IPS and Polars can elucidate the primary effects of the magnetic fields on the dynamics and thermodynamics in accreting white dwarf systems.

Imamura, James N.↗
DOE OSTI2022

ELECTRIC FIELD-ASSISTED DIFFUSION WELDING TO FABRICATE ALLOY 617 COMPACT HEAT EXCHANGERS

Compact heat exchangers are of interest for a number of applications including advanced reactors. Alloy 617 is one of the top candidate materials for the gas-cooled reactor intermediate heat exchanger. Previous endeavors to diffusion weld Alloy 617 utilized hot pressing (HP). It was reported that grain boundary migration across the interface was hindered by extensive precipitation. Bonds of this nature have been observed to reduce the elevated-temperature mechanical properties compared to the wrought-product form. It was hypothesized that the electric current applied during electric-field-assisted sintering (EFAS) can overcome these challenges, resulting in improved diffusion welding (DW). This study investigated DW of Alloy 617 via EFAS. Stacks composed of three sheets that were 20 mm in diameter were welded using EFAS. Specimens were welded with an applied electric current, a pressure of 30 MPa, hold time of 30 min, and temperatures of 1050°C, 1100°C, and 1150°C. DW using HP as the zero-current analog of EFAS was also performed at the most promising EFAS conditions. Results revealed that both the applied electric current and temperature played a key role in precipitation and grain boundary migration in diffusion-welded Alloy 617. Precipitates were observed at the interface of the hot-pressed samples which limited grain boundary migration. Electric current was found to prevent precipitate formation along the interface at 1150°C. The electric current coupled with a temperature of 1150°C during EFAS resulted in significant grain boundary migration across the interface.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Toward Consistent High-Fidelity Quantum Learning on Unstable Devices via Efficient In-Situ Calibration

In the near-term noisy intermediate-scale quantum (NISQ) era, high noise will significantly reduce the fidelity of quantum computing. What's worse, recent works reveal that the noise on quantum devices is not stable, that is, the noise is dynamically changing over time. This leads to an imminent challenging problem: At run-time, is there a way to efficiently achieve a consistent high-fidelity quantum system on unstable devices? To study this problem, we take quantum learning (a.k.a., variational quantum algorithm) as a vehicle, which has a wide range of applications, such as combinatorial optimization and machine learning. A straightforward approach is to optimize a variational quantum circuit (VQC) with a parameter-shift approach on the target quantum device before using it; however, the optimization has an extremely high time cost, which is not practical at run-time. To address the pressing issue, in this paper, we proposed a novel quantum pulse-based noise adaptation framework, namely QuPAD. In the proposed framework, first, we identify that the CNOT gate is the fidelity bottleneck of the conventional VQC, and we employ a more robust parameterized multi-qubit gate (i.e., Rzx gate) to replace CNOT gate. Second, by benchmarking Rzx gate with different parameters, we build a fitting function for each coupling qubit pair, such that the deviation between the theoretic output of Rzx gate and its on-device output under a given pulse amplitude and duration can be efficiently predicted. On top of this, an evolutionary algorithm is devised to identify the pulse amplitude and duration of each Rzx gate (i.e., calibration) and find the quantum circuits with high fidelity. Experiments show that the runtime on quantum devices of QuPAD with 8–10 qubits is less than 15 minutes, which is up to 270 x faster than the parameter-shift approach. In addition, compared to the vanilla VQC as a baseline, QuPAD can achieve 59.33% accuracy gain on a classification task, and average 66.34% closer to ground state energy for molecular simulation.

Hu, Zhirui↗
DOE OSTI2020

Active Learning Accelerated Discovery of Stable Iridium Oxide Polymorphs for the Oxygen Evolution Reaction

The discovery of high-performing and stable materials for sustainable energy applications is a pressing goal in catalysis and materials science. Understanding the relationship between a material’s structure and functionality is an important step in the process, such that viable polymorphs for a given chemical composition need to be identified. Machine-learning-based surrogate models have the potential to accelerate the search for polymorphs that target specific applications. Herein, we report a readily generalizable active-learning (AL) accelerated algorithm for identification of electrochemically stable iridium oxide polymorphs of IrO 2 and IrO 3 . The search is coupled to a subsequent analysis of the electrochemical stability of the discovered structures for the acidic oxygen evolution reaction (OER). Structural candidates are generated by identifying all 956 structurally unique AB2 and AB3 prototypes in existing materials databases (more than 38000). Next, using an active learning approach, we find 196 IrO 2 polymorphs within the thermodynamic amorphous synthesizability limit and reaffirm the global stability of the rutile structure. We find 75 synthesizable IrO 3 polymorphs and report a previously unknown FeF 3 -type structure as the most stable, termed α-IrO 3 . To test the algorithms performance, we compare to a random search of the candidate space and report at least a 2-fold increase in the rate of discovery. Additionally, the AL approach can acquire the most stable polymorphs of IrO 2 and IrO 3 with fewer than 30 density functional theory optimizations. Analysis of the structural properties of the discovered polymorphs reveals that octahedral local coordination environments are preferred for nearly all low-energy structures. Subsequent Pourbaix Ir–H 2 O analysis shows that α-IrO3 is the globally stable solid phase under acidic OER conditions and supersedes the stability of rutile IrO 2 . Calculation of theoretical OER surface activities reveal ideal weaker binding of the OER intermediates on α-IrO 3 than on any other considered iridium oxide. We emphasize that the proposed AL algorithm can be easily generalized to search for any binary metal oxide structure with a defined stoichiometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Numerical modeling of the interstellar medium in galactic disks

We have been developing detailed hydrodynamic models of the global interstellar medium in the hope of understanding the mass and volume occupied by various phases, as well as their structure and kinematics. In our model, the gas is modeled by one fluid while representative Pop 1 stars are modeled by a second fluid. The two fluids are coupled in that the gas forms into stars at a rate given by a Schmidt law while stellar mass loss returns matter into the gas phase (on a time scale of 100 Myr). Also, the stars heat the gas through stellar winds and the gas cools through optically thin radiation. The time behavior of these two fluids is studied in two spatial dimensions with the Eulerian finite difference numerical hydrodynamic code Zen. The two spatial dimensions are along the plane of a disk (x, total length of 2 kpc) and perpendicular to the disk (z, total height of +/- 15 kpc) and a galactic gravitational field in the z direction, typical of that at the solar circle, is imposed upon the simulation; self-gravity and rotation are absent. For the boundary conditions, outflow is permitted at the top and bottom of the grid (z = +/- 15 kpc) while periodic boundary conditions are imposed upon left and right sides of the grid. As initial conditions, we assumed a gaseous distribution like that seen for the H1 by earlier researchers, although the results are insensitive to the initial conditions. We have run simulations in which the heating due to stars, parameterized as a stellar wind velocity, a, is varied from low (a = 150 km/s), to intermediate (a = 300 km/s), to high (a = 600 km/s). Since the intermediate case is roughly equivalent to the Galactic energy injection rate from supernovae, this summary will concentrate on results from this simulation.

Rosen, A.↗
DOE OSTI2024

Mechanisms and site requirements for NO and NH 3 oxidation on Cu/SSZ-13

Two series of Cu/SSZ-13 catalysts were synthesized via aqueous solution and solid-state ion exchange using SSZ-13 supports of varying Si/Al ratios. The isolated and multinuclear Cu content of these catalysts were determined by H 2 temperature programmed reduction (H 2 -TPR). Multinuclear Cu in these catalysts, including in situ Cu- dimers formed from ZCu II OH coupling and permanent CuO clusters, are active species for dry NO oxidation. NH 3 oxidation on these catalysts follows an internal SCR (i-SCR) mechanism, i.e., a portion of NH 3 is first oxidized to NO, then NO is selectively reduced by the remaining NH 3 to N 2 . NH 3 oxidation displays distinct kinetic behavior below ~300 °C and above ~400 °C. At low temperature the results indicate that NH 3 -solvated mobile Cu-ions are the active centers. CuO clusters, when present, also contribute to the low temperature activity by catalyzing NH 3 oxidation to NO. At high temperature, in situ Cu-dimers and CuO clusters catalyze NH 3 oxidation to NO, and isolated Cu-ions catalyze SCR to realize the cascade turnovers. For both NO and NH 3 oxidation, Cu-dimers balanced by framework charges of close proximity appear to be more active than Cu-dimers balanced by distant framework charges. However, the former Cu-dimers are less stable than the latter and tend to split into monomers in the presence of vicinal Brønsted acid sites. Via density functional theory (DFT) calculations, the i-SCR mechanism for low temperature NH 3 oxidation, i.e., the energetic favorability for the involvement of the NO intermediate, is justified. Furthermore, the DFT results also agree with experimental data that the formation of Cu-dimers from ZCu II OH dimerization is essential for NH 3 oxidation at high temperature.

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

Investigation of giant Kerr nonlinearity in quantum cascade lasers using mid-infrared femtosecond pulses

We study the Kerr nonlinearity of quantum cascade lasers (QCLs) by coupling resonant and off-resonant mid-infrared (mid-IR) femtosecond (fs) pulses into an active QCL waveguide. We observe an increase in the spectral width of the transmitted fs pulses as the coupled mid-infrared (mid-IR) pulse power increases. This is explained by the self-phase modulation effect due to the large Kerr nonlinearity of QCL waveguides. We further confirm this effect by observing the intensity dependent far-field profile of the transmitted mid-IR pulses, showing the pulses undergo self-focusing as they propagate through the active QCL due to the intensity dependent refractive index. We experimentally estimate the nonlinear refractive index n{sub 2} of a QCL to be ∼8 × 10{sup −9 }cm{sup 2}/W using the far-field beam profile of the transmitted pulses. The finite-difference time-domain simulations of QCL waveguides with Kerr nonlinearity incorporated show similar behavior to the experimental results.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

The multichannel $n$-propyl + O 2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

The n-propyl + O 2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O 2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O 2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol -1 and 2.4 kcal mol -1 below the reactants, respectively. Two competitive $β$-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol -1 , a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol -1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction ($Δ$ DBOC = 1.71 kcal mol -1 ), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol -1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the $n$-propyl + O 2 potential energy surface provide key benchmarks for future studies of hydrocarbon oxidation.

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

Acetylene Semi-Hydrogenation on a Perovskite Oxyhydride Surface: Insights from First Principles and Microkinetic Modeling

Although perovskite oxyhydrides (POHs) have shown promise as a support for selective hydrogenation, it is unknown if they themselves can catalyze alkyne semi-hydrogenation. Here, we use first-principles density functional theory, coupled with microkinetic modeling, to investigate acetylene semi-hydrogenation on a prototypical POH, cubic BaTiO 2.5 H 0.5 (BTOH). Two different mechanisms are examined on a representative surface of BTOH under the reaction conditions: both are based on the Horiuti–Polanyi mechanism, but the way of H 2 dissociation is different. In mechanism 1, a lattice hydride H atom and then a surface adsorbed H atom sequentially hydrogenate the adsorbed acetylene. In mechanism 2, two lattice hydride H atoms from the BTOH sequentially hydrogenate the adsorbed acetylene. In both mechanisms, the H atoms are replenished from gas phase H 2 dissociation. Using density functional theory (DFT), we have calculated pathways for these two mechanisms in hydrogenation of acetylene to ethylene, as well as further to ethane. Microkinetic modeling based on the DFT energetics indicates that at 523 K, hydrogenation to ethylene and ethane via mechanism 1 occurs at a rate up to two orders of magnitude faster than via mechanism 2. A selectivity analysis for the temperature range of 373–673 K shows that the product observed is essentially only ethylene within the more active mechanism 1. This is because at the steady state, there is a significant amount of surface anion vacancies that facilitate heterolytic H 2 dissociation and help stabilize a vinyl intermediate. In conclusion, the present findings suggest that POHs are capable of selective hydrogenation, thanks to their rich hydrogen surface-redox chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

POROSITIES OF PROTOPLANETARY DUST AGGLOMERATES FROM COLLISION EXPERIMENTS

The aggregation of dust through sticking collisions is the first step of planet formation. The basic physical properties of the evolving dust aggregates strongly depend on the porosity of the aggregates; e.g., mechanical strength, thermal conductivity, and the gas-grain coupling time. Also, the outcome of further collisions depends on the porosity of the colliding aggregates. In laboratory experiments we study the growth of large aggregates of {approx}3 mm to 3 cm through continuous impacts of small dust agglomerates of 100 {mu}m in size, consisting of {mu}m grains at different impact velocities. The experiments show that agglomerates grow by direct sticking as well as through gravitational reaccretion. The latter can be regarded as a suitable analog to the reaccretion of fragments by gas drag in protoplanetary disks. Experiments were carried out in the velocity range between 1.5 m s{sup -1} and 7 m s{sup -1}. With increasing impact velocities the volume filling factor of the resulting agglomerates increases from {phi} = 0.2 for 1.5 m s{sup -1} to {phi} = 0.32 for 7 m s{sup -1}. These values are independent of the target size. Extrapolation of the measured velocity dependence of the volume filling factor implies that higher collision velocities will not lead to more compact aggregates. Therefore, {phi} = 0.32 marks a degree of compaction suitable for describing structures forming at v > 6 m s{sup -1}. At small collision velocities below 1 m s{sup -1}, highly porous structures with {phi} Almost-Equal-To 0.10 will form. For intermediate collision velocities porosities vary. Depending on the disk model and resulting relative velocities, objects in protoplanetary disks up to decimeters in size might evolve from highly porous ({phi} Almost-Equal-To 0.10) to compact ({phi} = 0.32) with a more complex intermediate size range of varying porosity.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

Hydrotreating Pyrolytic Lignin to Produce a Refinery Feedstock (Poster)

Fast pyrolysis of biomass followed by water separation to produce pyrolytic lignin and hydrotreating of the lignin could be used to produce a stable volatile low-oxygen intermediate liquid. Such a liquid could be converted into a finished motor-fuel in a refinery, taking advantage of the existing infrastructure and economies of scale of refineries. Hydrotreating just the lignin would consume less hydrogen while preserving about half of the energy of the original oil. The aqueous by-products could be reformed to produce the needed hydrogen and would contain much of the unwanted acids and unstable oxygenates. To assess such intermediate liquids, several pyrolytic lignins were prepared by mixing pyrolysis oil with water at 1:1 and 3:1 ratios. The carboxylic acidity in the pyrolytic lignin was reduced to 24 and 10 mg-KOH/g-lignin compared to 81 in the whole oil. These lignins were hydrotreated using Ni-Mo(S)/alumina, Pt/char, or Pd/C(activated) in a semi-batch 1 L stirred autoclave. The oil was stabilized under hydrogen at 150-280 degrees C, then water and light organics were removed by partial depressurization. Hydrodeoxygenation was then performed at 340-400 degrees C. Total pressure was controlled at 70 or 170 bar with hydrogen gas. Organic liquid yields of 39-56% were obtained. For many experiments the organic oxygen content was <7%, acidity was < 7 mg-KOH/g-oil, the volatility was greater than or equal to 94% and, on a carbon basis, the total yield of organic products miscible in hydrocarbons at a 1:10 ratio was over 50%. These properties are probably acceptable to a refinery.The residual liquids left in the reactor at the end of the experiment comprised 60-85% of the organic-phase product while the rest was condensate. 13C-NMR of the residual liquids showed that they were 50-80% aliphatic. 13C-NMR coupled with GC-MS identified phenolic compounds as the main oxygenates in most residual liquids.

09 BIOMASS FUELS↗
DOE OSTI2023

Isotope Effects in the Zundel–Eigen Isomerization of H + (H 2 O) 6

The isomerization pathway between the energetically low-lying Zundel and Eigen isomers of the protonated water hexamer was investigated using high-level ab initio calculations including a treatment of zero-point corrections. On the basis of these calculations, the Zundel–Eigen isomerization was found to proceed through a stable intermediate isomer, which consists of a four-membered ring with two single acceptor water molecules. Further, the inclusion of vibrational zero-point energy is shown to be important for accurately establishing the relative energies of the three relevant isomers involved in the Zundel–Eigen isomerization. Diffusion Monte Carlo calculations including anharmonic vibrational effects show that all three isomers of H + (H 2 O) 6 and D + (D 2 O) 6 have well-defined structures. The energetic ordering of the three isomers changes upon deuteration. The implications of these results for the vibrational spectra of H + (H 2 O) 6 and D + (D 2 O) 6 are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

NiAu single atom alloys for the selective oxidation of methacrolein with methanol to methyl methacrylate

In this work, the oxidative cross-coupling of unsaturated aldehydes and alcohols with methanol is catalyzed by O-activated gold surfaces in both ambient pressure and UHV conditions. From liquid-phase studies it has been found that either the addition of a base or the use of a basic support is necessary for high yields of the corresponding methyl ester. Here we demonstrate that addition of a small amount of Ni, at the single atom limit, on supported Au nanoparticles, without the aid of a base in the reaction solution or the use of a basic support, is sufficient to activate Au for the selective oxidative esterification of methacrolein with methanol. The Ni concentration and dispersion are followed by ICP-AES and in situ DRIFTS, respectively. The active site appears to be the same for both NiAu and Au NPs; namely, an [Au-O x ]- species, as similar apparent activation energies of the reaction were found in kinetic studies over these two catalysts. Ni was also shown to allow for lower methanol concentrations to be used without affecting the catalytic activity and selectivity to the desired product, methyl methacrylate. In situ vibrational spectroscopy studies were conducted in an ATR-IR cell, where the reaction progress was monitored by detecting the gradual conversion of adsorbed reactants on the catalytic surface to intermediates and finally to the desired product, which was produced at close to 100% selectivity at conversions exceeding 25% at 60 C on NiAu single atom alloy nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

H2@Scale: Technical and Economic Potential of Hydrogen as an Energy Intermediate

The H2@Scale concept is focused on developing hydrogen as an energy carrier and using hydrogen's properties to improve the national energy system. Specifically hydrogen has the abilities to (1) supply a clean energy source for industry and transportation and (2) increase the profitability of variable renewable electricity generators such as wind turbines and solar photovoltaic (PV) farms by providing value for otherwise potentially-curtailed electricity. Thus the concept also has the potential to reduce oil dependency by providing a low-carbon fuel for fuel cell electric vehicles (FCEVs), reduce emissions of carbon dioxide and pollutants such as NOx, and support domestic energy production, manufacturing, and U.S. economic competitiveness. The analysis reported here focuses on the potential market size and value proposition for the H2@Scale concept. It involves three analysis phases: 1. Initial phase estimating the technical potential for hydrogen markets and the resources required to meet them; 2. National-scale analysis of the economic potential for hydrogen and the interactions between willingness to pay by hydrogen users and the cost to produce hydrogen from various sources; and 3. In-depth analysis of spatial and economic issues impacting hydrogen production and utilization and the markets. Preliminary analysis of the technical potential indicates that the technical potential for hydrogen use is approximately 60 million metric tons (MMT) annually for light duty FCEVs, heavy duty vehicles, ammonia production, oil refining, biofuel hydrotreating, metals refining, and injection into the natural gas system. The technical potential of utility-scale PV and wind generation independently are much greater than that necessary to produce 60 MMT / year hydrogen. Uranium, natural gas, and coal reserves are each sufficient to produce 60 MMT / year hydrogen in addition to their current uses for decades to centuries. National estimates of the economic potential of hydrogen production using steam methane reforming of natural gas, high temperature electrolysis coupled with nuclear power plants, and low temperature electrolysis are reported. To generate the estimates, supply curves for those technologies are used. They are compared to demand curves that describe the market size for hydrogen uses and willingness to pay for that hydrogen. Scenarios are developed at prices where supply meets demand and are used to estimate energy use, emissions, and economic impacts.

13 HYDRO ENERGY↗
DOE OSTI2020

Experimental and DFT Calculated IR Spectra of Guests in Zeolites: Acyclic Olefins and Host-Guest Interactions

We performed experimental and periodic density functional theory (DFT) IR spectroscopy to investigate the adsorption of acyclic olefins over both acidic and non-acidic zeolites. Two conjugated polyenes, 2,4-dimethyl-1,3-pentadiene (I) and 2,6-dimethyl-2,4,6-octatriene (II) were studied to probe organic intermediates that can form during methanol conversion, and that can lead to deactivating species known collectively as “coke.” We computed vibrational spectra using zeolite-adsorbed and gas-phase models for both neutral and protonated forms of I and II, and compared these DFT results to diffuse reflectance IR Fourier transform (DRIFT) spectra of zeolite-guest systems. Our experimental and computational results are precise enough to pinpoint that the gauche s-cis conformation of species I predominates during adsorption over de-aluminated zeolite beta. Computed zeolite-adsorbed spectra of the protonated species I and II best represent the DRIFT spectra obtained after the adsorption of the olefins on HMOR at 20 ?, with computed bands at 1543 and 1562 cm–1 for molecules I+ and II+, respectively, attributed to the allylic stretching mode, ?(C=C–C+). These computed band frequencies are within 6 cm–1 of experimental data and confirm that the interaction between neutral acyclic olefins and acidic zeolites leads to protonation of the olefin. Comparison of computed spectra of the protonated species in the gas phase to those in the zeolite indicates that the electrostatic interaction between alkenyl and alkadienyl cations and negative zeolite framework does not significantly impact the position of the allylic stretching bands. These results highlight that computed spectroscopy and thermodynamics coupled with experimental spectra can be used for elucidating complex mixtures in zeolites, and certain spectral features of adsorbed olefins can be accurately modeled by gas-phase calculations. ACKNOWLEDGMENTS BM and SMA were supported by the National Science Foundation under Award # CBET-1512442. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support (or partial support) of this research (#589978-ND5, EDH and FCJ). MDB was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Materials Science and Engineering. CJM was supported by the DOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated by Battelle for the U.S. DOE. Computing resources were generously provided through PNNL’s institutional computing (PIC).

Manookian, Babgen↗
NASA NTRS1994

The RSA survey of dwarf galaxies, 1: Optical photometry

We present detailed surface photometry, based on broad B-band charge coupled device (CCD) images, of about 80 dwarf galaxies. Our sample represents approximately 10% of all dwarf galaxies identified in the vicinity of Revised Shapley-Ames (RSA) galaxies on high resolution blue photographic plates, referred to as the RSA survey of dwarf galaxies. We derive global properties and radial surface brightness profiles, and examine the morphologies. The radial surface brightness profiles of dwarf galaxies, whether early or late type, display the same varieties in shape and complexity as those of classical giant galaxies. Only a few are well described by a pure r(exp 1/4) law. Exponential profiles prevail. Features typical of giant disk galaxies, such as exponential profiles with a central depression, lenses, and even, in one case (IC 2041), a relatively prominent bulge are also found in dwarf galaxies. Our data suggest that the central region evolves from being bulge-like, with an r(exp 1/4) law profile, in bright galaxies to a lens-like structure in dwarf galaxies. We prove detailed surface photometry to be a helpful if not always sufficient tool in investigating the structure of dwarf galaxies. In many cases kinematic information is needed to complete the picture. We find the shapes of the surface brightness profiles to be loosely associated with morphological type. Our sample contains several new galaxies with properties intermediate between those of giant and dwarf ellipticals (but no M32-like objects). This shows that such intermediate galaxies exist so that at least a fraction of early-type dwarf ellipticals is structurally related to early-type giants instead of belonging to a totally unrelated, disjunct family. This supports an origin of early-type dwarf galaxies as originally more massive systems that acquired their current morphology as a result of substantial, presumable supernova-driven, mass loss. On the other hand, several early-type dwarfs in our sample are merger candidates. Merger events may lead to anisotropic velocity distributions in systems of any luminosity, including dwarfs. The RSA sample of dwarf galaxies is more likely to contain mergers because, in contrast to earlier dwarf galaxy surveys that have focused on clusters and rich groups of galaxies, the RSA dwarfs are typically located in low density environments. The occurrence of mergers among dwarf galaxies is of interest in connection with the rapid evolution of faint blue galaxy counts at redshift z less than 1 which suggests that dwarf galaxies were about five times more numerous in the recent past. Finally, our sample contains several examples of late-type dwarfs and 'transition' types that are potential precursors of nucleated early-type dwarfs. All the above processes--mass loss, mergers, astration--are likely to have contributed to the formation of the current population of diffuse early-type dwarfs. A few new redshifts of dwarf galaxies are reported in this paper.

Vader, J. Patricia↗
DOE OSTI2013

Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO 2 . We have shown that SRB reduce U(VI) to nanometer-sized UO 2 particles (1-5 nm) which are both intra- and extracellular, with UO 2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO 2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phase when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO 2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO 2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO 2 reoxidation with an initial rate of 9.5 M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO 2 reoxidation with ferrihydrite. The highest rate of UO 2 reoxidation occurred when the chelator promoted UO 2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO 2 dissolution did not occur, UO 2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO 2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO 2 reoxidation as Fe(III) oxidizes HS– preferentially over UO 2 . The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO 2 ) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO 2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.

54 ENVIRONMENTAL SCIENCES↗