Search NASA⌕ Search

SEARCH · Search NASA

Results for “INTERMEDIATE COUPLING”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

High fidelity simulation and analysis of liquid jet atomization in a gaseous crossflow at intermediate Weber numbers

Recent advances in numerical methods coupled with the substantial enhancements in computing power and the advent of high performance computing have presented first principle, high fidelity simulation as a viable tool in the prediction and analysis of spray atomization processes. The credibility and potential impact of such simulations, however, has been hampered by the relative absence of detailed validation against experimental evidence. The numerical stability and accuracy challenges arising from the need to simulate the high liquid-gas density ratio across the sharp interfaces encountered in these flows are key reasons for this. In this work we challenge this status quo by presenting a numerical model able to deal with these challenges, employing it in simulations of liquid jet in crossflow atomization and performing extensive validation of its results against a carefully executed experiment with detailed measurements in the atomization region. We then proceed to the detailed analysis of the flow physics. The computational model employs the coupled level set and volume of fluid approach to directly capture the spatiotemporal evolution of the liquid-gas interface and the sharp-interface ghost fluid method to stably handle high liquid-air density ratio. Adaptive mesh refinement and Lagrangian droplet models are shown to be viable options for computational cost reduction. Moreover, high performance computing is leveraged to manage the computational cost. The experiment selected for validation eliminates the impact of inlet liquid and gas turbulence and focuses on the impact of the crossflow aerodynamic forces on the atomization physics. Validation is demonstrated by comparing column surface wavelengths, deformation, breakup locations, column trajectories and droplet sizes, velocities, and mass rates for a range of intermediate Weber numbers. Analysis of the physics is performed in terms of the instability and breakup characteristics and the features of downstream flow recirculation, and vortex shedding. Formation of “Λ” shape windward column waves is observed and explained by the combined upward and lateral surface motion. The existence of Rayleigh-Taylor instability as the primary mechanism for the windward column waves is verified for this case by comparing wavelengths from the simulations to those predicted by linear stability analyses. Physical arguments are employed to postulate that the type of instability manifested may be related to conditions such as the gas Weber number and the inlet turbulence level. The decreased column wavelength with increasing Weber number is found to cause enhanced surface stripping and early depletion of liquid core at higher Weber number. A peculiar “three-streak-two-membrane” liquid structure is identified at the lowest Weber number and explained as the consequence of the symmetric recirculation zones behind the jet column. It is found that the vortical flow downstream of the liquid column resembles a von Karman vortex street and that the coupling between the gas flow and droplet transport is weak for the conditions explored.

42 ENGINEERING↗
DOE OSTI2014

Two-particle correlations in a dynamic cluster approximation with continuous momentum dependence: Superconductivity in the two-dimensional Hubbard model

The DCA + algorithm was recently introduced by Stear, Maier, and Schulthess [Phys. Rev. B 88, 115101 (2013), 10.1103/PhysRevB.88.115101] to extend the dynamic cluster approximation (DCA) with a continuous lattice self-energy in order to achieve better convergence with cluster size. In this work, we extend the DCA + algorithm to the calculation of two-particle correlation functions by introducing irreducible vertex functions with continuous momentum dependence consistent with the DCA + self-energy. This enables a significantly more controlled and reliable study of phase transitions than with the DCA. We test the new method by calculating the superconducting transition temperature $T_c$ in the attractive Hubbard model and show that it reproduces previous determinantal quantum Monte Carlo results. We then calculate $T_c$ in the doped repulsive Hubbard model, for which previous DCA calculations could only access the weak-coupling ($\textit{U}$ =4$\textit{t}$) regime for large clusters. Here, we show that the new algorithm provides access to much larger clusters and delivers asymptotically converged results for $T_c$ for both the weak ($\textit{U}$ =4$\textit{t}$) and intermediate ($\textit{U}$ =7$\textit{t}$) coupling regimes, and thereby enables the accurate determination of the exact infinite cluster size result.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1973

Computer program for determining rotational line intensity factors for diatomic molecules

A FORTRAN IV computer program, that provides a new research tool for determining reliable rotational line intensity factors (also known as Honl-London factors), for most electric and magnetic dipole allowed diatomic transitions, is described in detail. This users manual includes instructions for preparing the input data, a program listing, detailed flow charts, and three sample cases. The program is applicable to spin-allowed dipole transitions with either or both states intermediate between Hund's case (a) and Hund's case (b) coupling and to spin-forbidden dipole transitions with either or both states intermediate between Hund's case (c) and Hund's case (b) coupling.

Whiting, E. E.↗
DOE OSTI2020

BCS-BEC crossover in a (t 2g ) 4 excitonic magnet

The condensation of spin-orbit-induced excitons in t 2 g 4 electronic systems is attracting considerable attention. At large Hubbard U , antiferromagnetism was proposed to emerge from the Bose-Einstein Condensation (BEC) of triplons ( J eff = 1 ). Furthermore, we show that even at intermediate U regimes, the spin-orbit exciton condensation is possible leading also to staggered magnetic order. The canonical electron-hole excitations (excitons) transform into local triplon excitations at large U , and this BEC strong coupling regime is smoothly connected to the intermediate U excitonic insulator region. We solved the degenerate three-orbital Hubbard model with spin-orbit coupling ( λ ) in one dimension using the density matrix renormalization group, while in two dimensions we use the Hartree-Fock approximation (HFA). Employing these techniques, we provide the full λ versus U phase diagrams for both one- and two-dimensional lattices. Our main result is that at intermediate Hubbard U , increasing λ at fixed U the system transitions from an incommensurate spin-density-wave metal to a Bardeen-Cooper-Schrieffer (BCS) excitonic insulator, with coherence length r coh of O ( a ) and O ( 10 a ) in 1 d and 2 d , respectively, with a being the lattice spacing. Further increasing λ , the system eventually crosses over to the BEC limit (with r coh ≪ a ).

1-dimensional systems↗
DOE OSTI2019

Synthetic Model Complex of the Key Intermediate in Cytochrome P450 Nitric Oxide Reductase

Fungal denitrification plays a crucial role in the nitrogen cycle and contributes to the total N 2 O emission from agricultural soils. Here, cytochrome P450 NO reductase (P450nor) reduces two NO to N 2 O using a single heme site. Despite much research, the exact nature of the critical "Intermediate I" responsible for the key N-N coupling step in P450nor is unknown. This species likely corresponds to a Fe-NHOH-type intermediate with an unknown electronic structure. Here we report a new strategy to generate a model system for this intermediate, starting from the iron(III) methylhydroxylamide complex [Fe(3,5-Me-BAFP)(NHOMe)] (1), which was fully characterized by 1 H NMR, UV-vis, electron paramagnetic resonance, and vibrational spectroscopy (rRaman and NRVS). Our data show that 1 is a high-spin ferric complex with an N-bound hydroxylamide ligand that is strongly coordinated (Fe–N distance, 1.918 Å; Fe-NHOMe stretch, 558 cm –1 ). Simple one-electron oxidation of 1 at –80 °C then cleanly generates the first model system for Intermediate I, [Fe(3,5-Me-BAFP)(NHOMe)] + (1 + ). UV–vis, resonance Raman, and Mössbauer spectroscopies, in comparison to the chloro analogue [Fe(3,5-Me-BAFP)(Cl)] + , demonstrate that 1 + is best described as an Fe III -(NHOMe)• complex with a bound NHOMe radical. Further reactivity studies show that 1 + is highly reactive toward NO, a reaction that likely proceeds via N–N bond formation, following a radical–radical-type coupling mechanism. Here our results therefore provide experimental evidence, for the first time, that an Fe III -(NHOMe)• electronic structure is indeed a reasonable electronic description for Intermediate I and that this electronic structure is advantageous for P450nor catalysis because it can greatly facilitate N–N bond formation and, ultimately, N 2 O generation.

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

Directing CO 2 electroreduction pathways for selective C 2 product formation using single-site doped copper catalysts

Manipulating the selectivity-determining step in post-C–C coupling is crucial for enhancing C 2 product specificity during electrocatalytic CO 2 reduction, complementing efforts to boost rate-determining step kinetics. Here we highlight the role of single-site noble metal dopants on Cu surfaces in influencing C–O bond dissociation in an oxygen-bound selectivity-determining intermediate, steering post-C–C coupling toward ethylene versus ethanol. Integrating theoretical and experimental analyses, we demonstrate that the oxygen binding strength of the Cu surface controls the favorability of C–O bond scission, thus tuning the selectivity ratio of ethylene-to-ethanol. The Rh-doped Cu catalyst with optimal oxygen binding energy achieves a Faradaic efficiency toward ethylene of 61.2% and an ethylene-to-ethanol Faradaic efficiency ratio of 4.51 at –0.66 V versus RHE (reversible hydrogen electrode). Integrating control of both rate-determining and selectivity-determining steps further raises ethylene Faradaic efficiency to 68.8% at 1.47 A cm -2 in a tandem electrode. Our insights guide the rational design of Cu-based catalysts for selective CO 2 electroreduction to a single C 2 product.

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

Computational and Experimental Mechanistic Insights into the Ethanol-to-Butanol Upgrading Reaction over MgO

The mechanism of ethanol upgrading to higher products is still under debate, especially regarding intermediate species and hydrogenation and dehydrogenation steps. In this work, we conducted a combined theoretical and experimental approach to contribute to this discussion. For such, detailed electronic structure density functional theory calculations (aiming at probing density of states, infrared spectra, geometric parameters, charge densities, and reaction energetics) and diffuse reflectance infrared Fourier transform spectroscopy experiments were carried out revealing the relevance of an appropriate combination of reactive surface sites to support the formation of several intermediates that are formed in the C-C coupling over MgO. The roles of Mg and O sites were also studied under an electronic perspective and different geometrical arrangements. We found that a kink configuration was the most adequate for ethanol to 1-butanol upgrading. Our calculations also gave us arguments to propose distinct reaction routes, whose mutual predominance would depend upon reaction temperature. At temperatures up to 573 K, the so-called β-route, which goes through scission of a Cβ-H bond and formation of an oxametallacycle-like intermediate, would dominate the coupling, whereas at higher temperatures, up to 673 K, a more usual Guerbet mechanism, via an aldol coupling step and then consecutive hydrogenations, would be expected. Here, the theoretical conclusions were followed by a careful experimental strategy using sequential experimental planning techniques in order to estimate accurate parameters with the lowest possible experimental load. Information from these different sources were coupled to develop a mathematical model for the rate of the ethanol upgrading reaction, using a Langmuir-Hinshelwood-Hougen-Watson approach. The developed and statistically validated model adequately described the experimental data at 673 K and 1.1 bar total pressure for ethanol partial pressures in the range from 0 to 20 kPa.

09 BIOMASS FUELS↗
DOE OSTI2017

Density matrix renormalization group study of a three-orbital Hubbard model with spin-orbit coupling in one dimension

Using the density matrix renormalization group technique we study the effect of spin-orbit coupling on a three-orbital Hubbard model in the (t 2 g ) 4 sector and in one dimension. Fixing the Hund coupling to a robust value compatible with some multiorbital materials, we present the phase diagram varying the Hubbard U and spin-orbit coupling λ, at zero temperature. Our results are shown to be qualitatively similar to those recently reported using the dynamical mean-field theory in higher dimensions, providing a robust basis to approximate many-body techniques. Among many results, we observe an interesting transition from an orbital-selective Mott phase to an excitonic insulator with increasing λ at intermediate U. In the strong U coupling limit, we find a nonmagnetic insulator with an effective angular momentum <(J eff ) 2 >≠0 near the excitonic phase, smoothly connected to the <(J eff ) 2 >=0 regime. In conclusion, we also provide a list of quasi-one-dimensional materials where the physics discussed in this paper could be realized.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Split Dirac Supersymmetry: An Ultraviolet Completion of Higgsino Dark Matter

Motivated by the observation that the Higgs quartic coupling runs to zero at an intermediate scale, we propose a new framework for models of split supersymmetry, in which gauginos acquire intermediate scale Dirac masses of $\sim 10^{8-11}$ GeV. Scalar masses arise from one-loop finite contributions as well as direct gravity-mediated contributions. Like split supersymmetry, one Higgs doublet is fine-tuned to be light. The scale at which the Dirac gauginos are introduced to make the Higgs quartic zero is the same as is necessary for gauge coupling unification. Thus, gauge coupling unification persists (nontrivially, due to adjoint multiplets), though with a somewhat higher unification scale $\gtrsim 10^{17}$ GeV. The $\mu$-term is naturally at the weak scale, and provides an opportunity for experimental verification. We present two manifestations of Split Dirac Supersymmetry. In the "Pure Dirac" model, the lightest Higgsino must decay through R-parity violating couplings, leading to an array of interesting signals in colliders. In the "Hypercharge Impure" model, the bino acquires a Majorana mass that is one-loop suppressed compared with the Dirac gluino and wino. This leads to weak scale Higgsino dark matter whose overall mass scale, as well as the mass splitting between the neutral components, is naturally generated from the same UV dynamics. We outline the challenges to discovering pseudo-Dirac Higgsino dark matter in collider and dark matter detection experiments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Electrocatalytic CN Coupling: Advances in Urea Synthesis and Opportunities for Alternative Products

Urea is an essential fertilizer produced through the industrial synthesis of ammonia (NH 3 ) via the Haber–Bosch process, which contributes ≈1.2% of global annual CO 2 emissions. Electrocatalytic urea synthesis under ambient conditions via CN coupling from CO 2 and nitrogen species such as nitrate (NO 3 − ), nitrite (NO 2 − ), nitric oxide (NO), and nitrogen gas (N 2 ) has gained interest as a more sustainable route. However, challenges remain due to the unclear reaction pathways for urea formation, competing reactions, and the complexity of the resulting product matrix. This review highlights recent advances in catalyst design, urea quantification, and intermediate identification in the CN coupling reaction for electrocatalytic urea synthesis. Furthermore, this review explores future prospects for industrial CN coupling, considering potential nitrogen and carbon sources and examining alternative CN coupling products, such as amides and amines.

Chemistry↗
DOE OSTI2021

Observable proton decay in flipped SU(5)

We explore proton decay in a class of realistic supersymmetric flipped SU(5) models supplemented by a U(1) R symmetry which plays an essential role in implementing hybrid inflation. Two distinct neutrino mass models, based on inverse seesaw and type I seesaw, are identified, with the latter arising from the breaking of U(1) R by nonrenormalizable superpotential terms. Depending on the neutrino mass model an appropriate set of intermediate scale color triplets from the Higgs superfields play a key role in proton decay channels that include p → (e + , μ + ) π 0 , p → (e + , μ + ) K 0 , p → $\bar v$π + , and p → $\bar v$K + . We identify regions of the parameter space that yield proton lifetime estimates which are testable at Hyper-Kamiokande and other next generation experiments. We discuss how gauge coupling unification in the presence of intermediate scale particles is realized, and a Z 4 symmetry is utilized to show how such intermediate scales can arise in flipped SU(5). Finally, we compare our predictions for proton decay with previous work based on SU(5) and flipped SU(5).

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Deciphering the Mechanism of Base-Triggered Conversion of Ammonia to Molecular Nitrogen and Methylamine to Cyanide

Here we report an in-depth investigation into the ammonia oxidation mechanism by the catalyst [Ru III (tpy)(dmabpy)NH 3 ] 3 + ([Ru(NH 3 )] 3 + ). Stoichiometric reactions of [Ru(NH 3 )] 3 + were carried out with exogenous noncoordinating bases to trigger a proposed redox disproportionation reaction, which was followed using variable-temperature NMR spectroscopy. An intermediate species was identified as a dinitrogen-bridged complex using 15 N NMR and Raman spectroscopy on isotopically labeled complexes. This intermediate is proposed to derive from coupling of nitridyl species formed upon sequential redox disproportion reactions. Acetonitrile displaces the dinitrogen bridge to yield free N 2 . DFT calculations support this lower-energy pathway versus that previously reported for ammonia oxidation by the parent [Ru III (tpy)(bpy)NH 3 ] 3 + complex. These experimental and computational results are consistent with the interpretation of redox disproportionation involving sequential hydrogen atom transfer reactions by an amide/aminyl intermediate, [Ru(NH 2 ) – ] + $\Leftrightarrow$ [Ru(NH 2 ) • ] + , formed upon deprotonation of the parent complex. Control experiments employing a large excess of ammonia as a base indicate this new proposed lower-energy pathway contributes to the oxidation of ammonia to dinitrogen in conditions relevant to electrocatalysis. In addition, analogous methylamine complexes, [Ru(NH 2 CH 3 )] 2 + /3 + , were prepared to further test the proposed mechanism. Treating [Ru(NH 2 CH 3 )] 3 + with a base cleanly yields two products [Ru(NH 2 CH 3 )] 2 + and [Ru(CN)] + in an ~3:1 ratio, fully consistent with the proposed cascade of hydrogen atom transfer reactions by an intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Machine Learning-Accelerated First-Principles Molecular Dynamics Reveals C–C Coupling Mechanisms toward Ethylene on Cu(100)

Here, the Cu(100) termination has been identified as the most effective facet for converting CO and CO 2 into ethylene. To enhance both the activity and selectivity of ethylene production, we perform machine-learning-accelerated, first-principles molecular dynamics simulations at 298 K in an explicit solvent at pH 7 to elucidate the C–C coupling mechanism─the critical reaction step in forming C 2+ products. Among the six potential C–C coupling pathways, the most feasible are CO* dimerization and CO – CHO* and CHO* – CHO* couplings. Using the computational hydrogen electrode method, we demonstrate that all three pathways are equally accessible at −0.6 V vs RHE. At a potential below −1.0 V vs RHE, the thermodynamic barriers for the CO – CHO* and CHO* – CHO* pathways become negligible. Our computational findings explain the experimental observations, particularly the absence of C 2+ products above −0.4 V vs RHE and the peaks in ethylene production near −0.6 and −1.0 V vs RHE. Since CHO* acts as a key intermediate common to both C–C coupling and CH 4 formation, we propose that suppressing CHO* hydrogenation would inhibit CH 4 pathways, thereby maximizing ethylene selectivity.

CO2 reduction↗
DOE OSTI2022

Exploration of the bio-analogous asymmetric C–C coupling mechanism in tandem CO 2 electroreduction

C–C coupling is a critical step of CO 2 fixation in constructing the carbon skeleton of value-added multicarbon products. The Wood–Ljungdahl pathway is an efficient natural process through which microbes transform CO 2 into methyl and carbonyl groups and subsequently couple them together. This asymmetric coupling mechanism remains largely unexplored in inorganic CO 2 electroreduction. Here we experimentally validate the asymmetric coupling pathway through isotope-labelled co-reduction experiments on a Cu surface where 13 CH 3 I and 12 CO are co-fed externally as the methyl and the carbonyl source, respectively. Isotope-labelled multicarbon oxygenates were detected, which confirms an electrocatalytic asymmetric coupling on the Cu surface. We further employed tandem Cu–Ag nanoparticle systems in which *CH x and *CO intermediates can be generated to achieve asymmetric C–C coupling for a practical CO 2 electroreduction. We found that the production of multicarbon oxygenates is correlated with the generation rate of two intermediate indicators, CH 4 and CO. By aligning their rates, the oxygenates generation rate can be maximized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Intermediate Bandgap Solar Cells From Nanostructured Silicon

This project aimed to demonstrate increased electronic coupling in silicon nanostructures relative to bulk silicon for the purpose of making high efficiency intermediate bandgap solar cells using silicon. To this end, we formed nanowires with controlled crystallographic orientation, small diameter, <111> sidewall faceting, and passivated surfaces to modify the electronic band structure in silicon by breaking down the symmetry of the crystal lattice. We grew and tested these silicon nanowires with <110>-growth axes, which is an orientation that should produce the coupling enhancement.

14 SOLAR ENERGY↗
DOE OSTI2014

Carrier behavior in special multilayer device composed of different transition metal oxide-based intermediate connectors

The impact of illumination on the connection part of the tandem organic light-emitting diodes was studied by using a special organic multilayer sample consisted of two organic active layers coupled with different transition metal oxide (TMO)-based intermediate connectors (ICs). Through measuring the current density-voltage characteristic, interfacial electronic structures, and capacitance-voltage characteristic, we observe an unsymmetrical phenomenon in current density-voltage and capacitance-voltage curves of Mg:Alq{sub 3}/MoO{sub 3} and MoO{sub 3} composed devices, which was induced by the charge spouting zone near the ICs region and the recombination state in the MoO{sub 3} layer. Moreover, Mg:Alq{sub 3}/MoO{sub 3} composed device displays a photovoltaic effect and the V{sub oc} shifts to forward bias under illumination. Our results demonstrate that the TMO-based IC structure coupled with photovoltaic effect can be a good approach for the study of photodetector, light sensor, and so on.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

A scalable framework for efficient coupling of thermal and microstructural simulations in additive manufacturing

Predicting microstructure evolution in metal additive manufacturing (AM) is important for process optimization, but spatiotemporal scale disparities between thermal transport and microstructure evolution create significant challenges for efficient data transfer between simulation codes. To address this, we present Stork, a scalable framework for coupling thermal and microstructural simulations. Stork uses a sparse data representation to identify and store active solidification sub-volumes, enabling highly parallel quad-linear interpolation from coarse thermal grids to fine microstructure grids without large intermediate storage. We demonstrate the framework by coupling the semi-analytic heat transfer code 3DThesis with the time-parallel cellular automata code Toucan. This approach achieves over two orders of magnitude reduction in data generation time and file size compared to prior workflows. Numerical studies show that quad-linear interpolation preserves grain morphology and crystallographic texture in laser powder bed fusion (LPBF) simulations for coarsening ratios up to 16. Overall, Stork provides a scalable pathway for high-throughput, component-scale AM simulations on modern high-performance computing systems.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Sequential Cascade Electrocatalytic Conversion of Carbon Dioxide to C–C Coupled Products

Cascade catalytic processes perform multistep chemical transformations without isolating the intermediates. Here, we demonstrate a sequential cascade pathway to convert CO 2 to C 2+ hydrocarbons and oxygenates in a two-step electrocatalytic process using CO as the intermediate. CO 2 to CO conversion is performed by using Ag, and further conversion of CO to C-C coupled products is performed with Cu. Temporal separation between the two reaction steps is accomplished by situating the Ag electrode upstream of the Cu electrode in a continuous flow reactor. Convection-diffusion simulations and experimental evaluation of the electrodes individually are performed to identify optimal conditions. With the upstream Ag electrode poised at -1 V versus reversible hydrogen electrode in a flow of CO 2 -saturated water in aqueous carbonate buffer, over 80% of the CO can be converted on the downstream Cu electrode. When the Ag electrode is on, a supersaturation of CO is achieved near the Cu electrode, which leads to a relative increase in the formation rate of C 2 and C 3 oxygenates as compared to ethylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗