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Results for “reversible computation”

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 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Cosmic ray transverse gradient for a Hale cycle

We have used neutron monitor data obtained at Deep River and Huancayo as well as the vertical underground telescope data obtained at Embudo to compute the cosmic ray transverse gradient (G(sub theta)) for the 1965 to 1990 period. The computed mean value of G(sub theta) for a given qA epoch, changes sign with the change in the solar magnetic polairty in accordance with the predictions of some contemporary hypotheses. Also, we find that the magnitude of G(sub theta) undergoes a significant time variation during a given polarity epoch. It has the largest value near the solar polar field reversal epoch boundaries, when magnetic polarity in the solar northern hemisphere is positive (qA greater than O). For each of the three solar polar field reversals, the change in the magnitude of G(sub theta) is steeper across the epoch boundaries. There is a good correlation between G(sub theta) and the tilt angle of the helisopheric neutral current sheet (HNCS). Our results are in agreement with the reported piecemeal measurements of the latitudinal gradient made by spacecrafts, at different times, at lower primary energies, at far off distances from Earth's orbit. As such, their global significace is appreciable. Even so, it is not clear yet how these findings reflect upon the drift hypothesis in its present form. However, they do affirm the important role played by the tilt angle of HNCS in the modulation processes.

Ahluwalia, H. S.↗
DOE OSTI2016

Asynchronous τ-leaping

Stochastic simulation of cell signaling pathways and genetic regulatory networks has contributed to the understanding of cell function; however, investigation of larger, more complicated systems requires computationally efficient algorithms. τ-leaping methods, which improve efficiency when some molecules have high copy numbers, either use a fixed leap size, which does not adapt to changing state, or recalculate leap size at a heavy computational cost. We present a hybrid simulation method for reaction-diffusion systems which combines exact stochastic simulation and τ-leaping in a dynamic way. Putative times of events are stored in a priority queue, which reduces the cost of each step of the simulation. For every reaction and diffusion channel at each step of the simulation the more efficient of an exact stochastic event or a τ-leap is chosen. This new approach removes the inherent trade-off between speed and accuracy in stiff systems which was present in all τ-leaping methods by allowing each reaction channel to proceed at its own pace. Both directions of reversible reactions and diffusion are combined in a single event, allowing bigger leaps to be taken. This improves efficiency for systems near equilibrium where forward and backward events are approximately equally frequent. Comparison with existing algorithms and behaviour for five test cases of varying complexity shows that the new method is almost as accurate as exact stochastic simulation, scales well for large systems, and for various problems can be significantly faster than τ-leaping.

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

Prediction of long-term (> 10 year) cardiovascular outcomes in heart transplant recipients: Value of stress technetium-99m tetrofosmin myocardial perfusion imaging

Background: Myocardial perfusion imaging (MPI) using single-photon emission computed tomography (SPECT) is useful in the evaluation of cardiac allograft vasculopathy (CAV) in heart transplant (HTx) recipients. The current study evaluated the long-term prognostic value of stress SPECT MPI for predicting all-cause mortality and cardiac events in HTx recipients. Methods: The study population consisted of 166 HTx recipients (mean age 54 ± 10 years, 84% male) who underwent exercise or dobutamine stress {sup 99m}Tc-tetrofosmin SPECT MPI for the assessment of CAV. An abnormal SPECT MPI was defined as the presence of a fixed or a reversible perfusion defect. Endpoints were all-cause mortality, cardiac mortality, and non-fatal myocardial infarction (MI). Results: MPI abnormalities were detected in 55 patients (33%), including fixed defects in 28 patients (17%), partially reversible in 17 patients (10%), and completely reversible defects in 10 patients (6%). During a median follow-up of 12.8 years (range 0-15, mean follow-up 9.5 years), 109 (66%) patients died (all-cause mortality), of which 67 (40%) were due to cardiac causes. A total of 5 (3%) patients experienced a non-fatal MI. HTx recipients with a normal stress {sup 99m}Tc-tetrofosmin SPECT MPI had a significantly better prognosis as compared with those with an abnormal study, up to 5 years after the initial test. The presence of a reversible perfusion defect was a significant predictor of all-cause mortality, cardiac mortality, and major cardiac events, during the entire follow-up period. Conclusions: Stress {sup 99m}Tc-tetrofosmin SPECT MPI provides valuable prognostic information for the prediction of long-term outcome in HTx recipients. Patients with a normal stress {sup 99m}Tc-tetrofosmin SPECT MPI have a significantly better prognosis as compared with those with an abnormal study, up to 5 years after initial testing.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2019

Role of surface reconstruction on Cu/TiO 2 nanotubes for CO 2 conversion

Carbon dioxide hydrogenation to CO via the reverse water gas shift (RWGS) reaction is one route to integrate CO 2 utilization into the chemical industry. TiO 2 supported Cu catalysts are known to be active for RWGS, but Cu is shown here to behave differently on TiO 2 nanotubes (TiNT) vs TiO 2 nanoparticles (TiNP). Whereas nanoparticle supports give low rates that are hardly changed by added Cu, the nanotube supports yield much higher activity and three distinct behaviors as the Cu surface density increases. At low surface densities (0.3 Cu/nm 2 ), active Cu-O-Ti sites are created that have low apparent activation energies. At high surface densities (6 Cu/nm 2 ), Cu nanoparticles on TiNT are formed, and reaction barriers are lowered when both Cu and TiNT surfaces are accessible. At intermediate surface densities, metallic Cu domains are engulfed by a TiOx overlayer formed during H 2 pretreatment, akin to those formed by classical strong metal support interactions (SMSI). These reduced layers are markedly more active for RWGS than the initial TiNT surfaces, but have similar activation barriers, which are higher than those for which both Cu and TiNP surfaces are exposed. These catalytic findings are supported by computational modeling, in situ IR, UV–vis, and X-ray absorption spectroscopies, and they provide insight into an important reaction for CO 2 utilization.

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

Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism

In this paper, the interconversion of molybdenum ethylene and ethyl complexes by proton-coupled electron transfer (PCET) is described, an unusual transformation in organometallic chemistry. The cationic molybdenum ethylene complex [( Ph Tpy)(PPh 2 Me) 2 Mo(C 2 H 4 )][BArF 24 ] ([1-C 2 H 4 ] + ; Ph Tpy = 4'-Ph-2,2',6',2"-terpyridine, ArF 24 = [C 6 H 3 -3,5-(CF 3 ) 2 ] 4 ) was synthesized, structurally characterized, and its electronic structure established by a combination of spectroscopic and computational methods. The overall electronic structure is best described as a molybdenum(III) complex with a metallacyclopropane and a redox neutral terpyridine ligand. Addition of the nonclassical ammine complex [( Ph Tpy)(PPh 2 Me) 2 Mo(NH 3 )][BArF 24 ] ([1-NH 3 ] + ) to [1-C 2 H 4 ] + resulted in a net C–H bond-forming PCET reaction to yield the molybdenum ethyl [( Ph Tpy)(PPh 2 Me) 2 Mo(CH 2 CH 3 )][BArF 24 ] ([1-CH 2 CH 3 ] + ) and amido [( Ph Tpy)(PPh 2 Me) 2 Mo(NH 2 )][BArF 24 ] ([1-NH 2 ] + ) compounds. The reaction was reversed by addition of 2,4,6-tritert-butylphenoxyl radical to [1-CH 2 CH 3 ] + . The solid-state structure of [1-CH 2 CH 3 ] + established a β-agostic ethyl ligand that is maintained in solution as judged by variable temperature 1 H and 13 C NMR experiments. A combination of variable-temperature NMR experiments and isotopic labeling studies were used to probe the dynamics of [1-CH 2 CH 3 ] + and established restricted β-agostic -CH 3 rotation at low temperature (ΔG ‡ = 9.8 kcal mol –1 at -86 °C) as well as ethyl isomerization by β-hydride elimination-olefin rotation-reinsertion (ΔH ‡ = 19.3 ± 0.6 kcal mol –1 ; ΔS ‡ = 3.4 ± 1.7 cal mol –1 K –1 ). The β-(C–H) bond-dissociation free energy (BDFE) in [1-CH 2 CH 3 ] + was determined experimentally as 57 kcal mol –1 (THF) supported by a DFT-computed value of 52 kcal/mol –1 (gas phase). Comparison of pK a and electrochemical data for the complexes [1-C 2 H 4 ] + and [1-NH 3 ] + in combination with a deuterium kinetic isotope effect (k H /k D ) of 3.5(2) at 23 °C support a PCET process involving initial electron transfer followed by protonation leading to the formation of [1-CH 2 CH 3 ] + and [1-NH 2 ] + or a concerted pathway. Lastly, the data presented herein provides a structural, thermochemical and mechanistic foundation for understanding the PCET reactivity of organometallic complexes with alkene and alkyl ligands.

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

Surface-Driven Evolution of the Anomalous Hall Effect in Magnetic Topological Insulator MnBi 2 Te 4 Thin Films

We report understanding the effects of the interfacial modification to the functional properties of magnetic topological insulator thin films is crucial for developing novel technological applications from spintronics to quantum computing. Here, a large electronic and magnetic response is reported to be induced in the intrinsic magnetic topological insulator MnBi 2 Te 4 by controlling the propagation of surface oxidation. It is shown that the formation of the surface oxide layer is confined to the top 1–2 unit cells but drives large changes in the overall magnetic response. Specifically, a dramatic reversal of the sign of the anomalous Hall effect is observed to be driven by finite thickness magnetism, which indicates that the film splits into distinct magnetic layers each with a unique electronic signature. These data reveal a delicate dependence of the overall magnetic and electronic response of MnBi 2 Te 4 on the stoichiometry of the top layers. This study suggests that perturbations resulting from surface oxidation may play a non-trivial role in the stabilization of the quantum anomalous Hall effect in this system and that understanding targeted modifications to the surface may open new routes for engineering novel topological and magnetic responses in this fascinating material.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tight-Binding Model Study of Anti-ferromagnetic Order in AA-Stacked Bi-layer Graphene

We address here the anti-ferromagnetic order present in AA-stacked bi-layer graphene in a transversely applied electric field. The system is described by kinetic energy with nearest-neighbor electron hopping with same hopping integral t{sub 1} for both the layers. Besides this, Coulomb interaction exists at A and B sub-lattices with same Coulomb correlation energy. The electron Green’s functions are calculated by Zubarev’s Green’s technique. The temperature-dependent anti-ferromagnetic magnetization is calculated from the Green’s function and is computed numerically and self-consistently. The strong on-site Coulomb interaction stabilizes the anti-ferromagnetic order in graphene. We assume that the electron spin at A site in the first layer is directed in the opposite direction to that of A site electron in the second layer. Similar spin order is observed for electrons in B site atom in reversed order. It is observed that anti-ferromagnetic (AFM) magnetization in the first layer nearly remains constant up to certain temperature and then increases with temperature, while the AFM magnetization in the second layer remains nearly constant and then rapidly decreases with temperature. The net AFM magnetization in bi-layer graphene remains constant and then rapidly increases with temperature. The evolution of the AFM magnetization is studied by varying transverse electric field, Coulomb energy, and temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes

The path to realizing low-cost, stable, and earth-abundant photoelectrodes can be enabled through a detailed understanding of the optoelectronic properties of these materials by combining theory and experimental techniques. Of the limited set of oxide photocathode materials currently available, CuFeO 2 has emerged as a promising candidate warranting detailed attention. Here, highly compact thin films of rhombohedral (3R) CuFeO 2 were prepared via reactive co-sputtering. Despite its 1.43 eV indirect band gap, a cathodic photocurrent of 0.85 mA/cm 2 was obtained at 0.4 V versus reversible hydrogen electrode in the presence of a sacrificial electron acceptor. This unexpected performance was related to inefficient bulk charge separation because of the ultrafast (<1 ps) self-trapping of photogenerated free carriers. The electronic structure of 3R-CuFeO 2 was elucidated through a combination of optical and X-ray spectroscopic techniques and further complemented by first-principles computational methods including a many-body approach for computing the O K-edge X-ray absorption spectrum. Through resonant inelastic X-ray scattering spectroscopy, the visible absorption edges of CuFeO 2 were found to correspond to Cu → Fe metal-to-metal charge transfer, which exhibits a high propensity toward self-trapping. Findings of the present work enable us to understand the performance bottlenecks of CuFeO 2 photocathodes and suggest feasible strategies for improving material limitations.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Suppression of one-dimensional weak localization by band asymmetry

Herein we investigate disorder-induced localization in metals that break time-reversal and inversion symmetries through their energy dispersion, ε k ≠ε– k , but lack Berry phases. In the perturbative regime of disorder, we show that weak localization is suppressed due to a mismatch of the Fermi velocities of left and right movers. To substantiate this analytical result, we perform quench numerics on chains shorter than the Anderson localization length ξ—the latter computed and verified to be finite using the recursive Green's function method—and find a sharp rise in the saturation value of the participation ratio due to band asymmetry, indicating a tendency to delocalize. Interestingly, for weak disorder strength η, we see a better fit to the scaling behavior ξ∝1/η 2 for asymmetric bands than conventional symmetric ones.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Ligand Exchange Kinetics of Environmentally Relevant Metals

The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237 Np is a radioactive transuranic element with a half-life of 2 million years.

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

Thermodynamics and Kinetics of Sulfur Cathode during Discharge in MgTFSI 2 -DME Electrolyte

Rechargeable magnesium/sulfur battery is of significant interest because its energy density (1700 Wh kg -1 and 3200 Wh L -1 ) is among the highest of all battery chemistries (lower than Li/O 2 and Mg/O 2 but comparable to Li/S), and Mg metal allows reversible operation (100% Coulombic efficiency) with no dendrite formation. This great promise is already justified in some early reports. However, lack of mechanistic study of sulfur reaction in the Mg cation environment has severely hindered our understanding and prevents effective measures for performance improvement. In this work, the very first systematic fundamental study on Mg/S system is conducted by combining experimental methods with computational approach. The thermodynamics and reaction pathway of sulfur cathode in MgTFSI 2 –DME electrolyte, as well as the associated kinetics are thoroughly investigated. The results here reveal that sulfur undergoes a consecutive staging pathway in which the formation and chain-shortening of polysulfide occur at early stage accompanied by the dissolution of long-chain polysulfide, and solid-state transition from short-chain polysulfide to magnesium sulfide occurs at late stage. Finally, the former process is much faster than the latter due to the synergetic effect of the mediating effect of dissolved polysulfide and the fast diffusion of Mg ion in the amorphous intermediate.

25 ENERGY STORAGE↗
DOE OSTI2013

MD simulations of phase stability of PuGa alloys: Effects of primary radiation defects and helium bubbles

We present classical molecular dynamics (MD) with Modified Embedded Atom Model (MEAM) simulations to investigate the role of primary radiation defects and radiogenic helium as factors affecting the phase stability of PuGa alloys in cooling–heating cycles at ambient pressure. The models of PuGa alloys equilibrated at ambient conditions were subjected to cooling–heating cycles in which they were initially cooled down to 100 K and then heated up to 500 K at ambient pressure. The rate of temperature change in the cycles was 10 K/ns. The simulations showed that the initial FCC phase of PuGa alloys undergo polymorphous transition in cooling to a lower symmetry α'-phase. All the alloys undergo direct and reverse polymorphous transitions in the cooling–heating cycles. The alloys containing vacancies shift in both transitions to lower temperatures relative to the defect-free alloys. The radiogenic helium has much less effect on the phase stability compared to that of primary radiation defects (in spite of the fact that helium concentration is twice of that for the primary radiation defects). Lastly, this computational result agrees with experimental data on unconventional stabilization mechanism of PuGa alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2024

On the prediction of pressure effects for the combination kinetics of two alkyl radicals with the geometric mean rule

Here, alkyl combination reactions, along with their reverse alkane unimolecular decomposition reactions, are widely present in pyrolysis and combustion systems. These reactions occur mainly at temperatures at which their rate coefficients depend on pressure, and only a few studies have explored this dependence for large size alkyls. The accurate calculation of these kinetic data is limited by the size of the alkyl fragments involved, since the theoretical methods used are computationally expensive. Therefore, little reliable data is available for the modeling of real fuels alkane decomposition kinetics. In this paper, we propose an alternative approach that allows an accurate estimation of pressure-dependent kinetic rates for the combination of long-chain alkyl radicals, based on tabulated reaction models. The rates of combination of linear alkyls radicals forming ethane to pentane were calculated using the CASPT2-F12/cc-pVDZ-F12 level within VRC-TST theory combined with master-equation simulations. The computed high-pressure limit rate coefficients showed that n-propyl could be a minimum-size representative structure for larger n-alkyl chain, but this approach fails to capture the pressure dependence of the reaction that remains size-dependent for larger alkyls. The Geometric Mean Rule (GMR), a simple rule that links the self and cross-reactions of three alkyl radicals, is used to address this issue. Our theoretical calculations show for the first time that the GMR applies not only at the high-pressure limit, but also for every pressure explored. The GMR is shown to be accurate, with a maximum 22 % deviation in the falloff region for the estimation of rates for small alkyl combinations. Using this method, we propose a tabulated reaction rate rule for the combination of alkyl radicals up to C5+C5. The use of computed rate coefficients with the GMR approximation opens ways to develop pressure-dependent reaction rate rules for large n-alkyl combinations, based on accurate and computationally expensive theoretical calculations on smaller alkyl fragments.

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

BASS: An R Package for Fitting and Performing Sensitivity Analysis of Bayesian Adaptive Spline Surfaces

In this work, we present the R package BASS as a tool for nonparametric regression. The primary focus of the package is fitting fully Bayesian adaptive spline surface (BASS) models and performing global sensitivity analyses of these models. The BASS framework is similar to that of Bayesian multivariate adaptive regression splines (BMARS) from Denison, Mallick, and Smith (1998), but with many added features. The software is built to efficiently handle significant amounts of data with many continuous or categorical predictors and with functional response. Under our Bayesian framework, most priors are automatic but these can be modified by the user to focus on parsimony and the avoidance of overfitting. If directed to do so, the software uses parallel tempering to improve the reversible jump Markov chain Monte Carlo (RJMCMC) methods used to perform inference. We discuss the implementation of these features and present the performance of BASS in a number of analyses of simulated and real data.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

A review of the shear rheology of carbon black suspensions

The microstructural link to the rheology of carbon black suspensions has recently become clear as a result of advances in computational and experimental methods. This understanding reveals the important role of the restructuring, build-up, and break-up of carbon black agglomerates in simple shear, rationalized by a dimensionless balance of the hydrodynamic forces acting to break the agglomerates apart against the cohesive forces holding them together (i.e., the Mason number). The Mason number not only can predict the origin of reversible thixotropy seen in carbon black suspensions observed at higher shear intensities, but can also be used to rationalize the evolution of microstructure at lower shear intensities. This review focuses on carbon black suspension behavior, but the insights derived from carbon black suspensions are broadly applicable to a diverse class of soft matter including colloidal gels relevant to a variety of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Aeroelastic stability of coupled flap-lag motion of hingeless helicopter blades at arbitrary advance ratios

Equations for large amplitude coupled flap-lag motion of a hingeless elastic helicopter blade in forward flight are derived. Only a torsionally rigid blade excited by quasi-steady aerodynamic loads is considered. The effects of reversed flow together with some new terms due to radial flow are included. Using Galerkin's method the spatial dependence is eliminated and the equations are linearized about a suitable equilibrium position. The resulting system of homogeneous periodic equations is solved using multivariable Floquet-Liapunov theory, and the transition matrix at the end of the period is evaluated by two separate methods. Computational efficiency of the two numerical methods is compared. Results illustrating the effects of forward flight and various important blade parameters on the stability boundaries are presented.

Friedmann, P.↗
NASA NTRS1995

Interaction of an interplanetary shock with the heliospheric plasma sheet

Interplanetary shocks often propagate along the heliospheric plasma sheet (HPS) where the interplanetary magnetic field (IMF) changes its polarity. This problem is investigated by the time-dependent 2.5-D MHD numerical model in the meridional plane. An example of computation is shown in the figure using density (log) contours and IMF vectors. Values of plasma parameters along the HPS fluctuate in time due to the Kelvin-Helmholtz instability. The HPS with its decreased intensity of the IMF as well as with its increased mass density causes a dimple in the shock structure (relatively weak for the forward shock, significant for the reverse shock, and very large for the contact discontinuity). Beyond the forward shock, the HPS is slightly compressed due to the post-shock increase of the azimuthal IMF component. Then follows expansion of the HPS surrounded by the highly-deformed contact discontinuity. A significant draping of IMF lines occurs around this structure that increases the meridional component of the IMF. This can cause a favorable condition for initiation of a geomagnetic storm.

Odstrcil, D.↗
DOE OSTI2018

Computational framework for modeling membrane processes without process and solution property simplifications

Accurately modeling membrane processes is critical to evaluating novel process configurations, designing scalable membrane systems, informing process cost estimates, and directing future research. Most membrane process models trade accuracy for computational efficiency by employing simplified approximations of the process (i.e. no salt flux, no pressure drop) and solution properties (i.e. ideal solution, and constant density, viscosity, and diffusivity). Our report introduces a detailed one-dimensional finite difference model for evaluating membrane processes that avoids these common simplifications. We apply this model to quantify the error introduced by these simplifications for case studies of reverse osmosis, osmotically assisted reverse osmosis, forward osmosis, and pressure retarded osmosis. While the magnitude of error introduced by these simplifications is reliant on the case study parameters and specifications, we find that existing model formulations can underestimate or overestimate average water flux by nearly 50% for some membrane processes operating under standard conditions. Lastly we investigate the error introduced by simplified inlet-outlet models that do not solve the governing system of differential equations, and we assess the accuracy of novel inlet-outlet formulations that use a log and geometric mean, instead of the typical arithmetic mean, to represent non-linear water flux profiles.

42 ENGINEERING↗