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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.

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At least 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

A divergent route to core- and peripherally functionalized diazacoronenes that act as colorimetric and fluorescence proton sensors

Combining core annulation and peripheral group modification, we have demonstrated a divergent synthesis of a family of highly functionalized coronene derivatives from a readily accessible dichlorodiazaperylene intermediate. Various reactions, such as aromatic nucleophilic substitution, Kumada coupling and Suzuki coupling proceed effectively on α-positions of the pyridine sites, giving rise to alkoxy, thioalkyl, alkyl or aryl substituted polycyclic aromatic hydrocarbons. In addition to peripheral group modulation, the aromatic core structures can be altered by annulation with thiophene or benzene ring systems. Corresponding single crystal X-ray diffraction and optical studies indicate that the heteroatom linkages not only impact the solid state packing, but also significantly influence the optoelectronic properties. Furthermore, these azacoronene derivatives display significant acid-induced spectroscopic changes, suggesting their great potential as colorimetric and fluorescence proton sensors.

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

Steering CO 2 electroreduction toward ethanol production by a surface-bound Ru polypyridyl carbene catalyst on N-doped porous carbon

Significance Electrochemical reduction of CO 2 can convert CO 2 emission back to value-added fuels and chemicals and store renewable electricity. Reducing CO 2 to multicarbon products has attracted great interest because of their higher energy densities and associated economic values. We report here a promising strategy for steering CO 2 electroreduction toward ethanol production by exploiting a surface-bound Ru polypyridyl carbene catalyst on an N-doped porous carbon electrode. We show the synergistic effects of Ru polypyridyl carbene for CO intermediate production with a porous carbon for C–C coupling that could boost ethanol production at relatively low overpotentials. The strategy provides insights on how to improve selectivity and efficiency for CO 2 reduction toward multicarbon products.

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

Preheating after multifield inflation with nonminimal couplings. III. Dynamical spacetime results

This paper concludes our semianalytic study of preheating in inflationary models comprised of multiple scalar fields coupled nonminimally to gravity. Using the covariant framework of paper I in this series, we extend here the rigid-spacetime results of paper II by considering both the expansion of the Universe during preheating, as well as the effect of the coupled metric perturbations on particle production. The adiabatic and isocurvature perturbations are governed by different effective masses that scale differently with the nonminimal couplings and evolve differently in time. The effective mass for the adiabatic modes is dominated by contributions from the coupled metric perturbations immediately after inflation. The metric perturbations contribute an oscillating tachyonic term that enhances an early period of significant particle production for the adiabatic modes, which ceases on a time scale governed by the nonminimal couplings ${{\xi}}_{I}$. The effective mass of the isocurvature perturbations, on the other hand, is dominated by contributions from the fields' potential and from the curvature of the field-space manifold (in the Einstein frame), the balance between which shifts on a time scale governed by ${{\xi}}_{I}$. As in papers I and II, we identify distinct behavior depending on whether the nonminimal couplings are small [${{\xi}}_{I}{\lesssim}\mathcal{O}(1)$], intermediate [${{\xi}}_{I}{\sim}\mathcal{O}(1{-}10)$], or large (${{\xi}}_{I}{\ge}100$).

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Dark Matter in the Heavens and at Colliders: Models and Constraints

In this dissertation, we investigate various aspects of dark matter detection and model building. Motivated by the cosmic ray positron excess observed by PAMELA, we construct models of decaying dark matter to explain the excess. Specifically we present an explicit, TeV-scale model of decaying dark matter in which the approximate stability of the dark matter candidate is a consequence of a global symmetry that is broken only by instanton-induced operators generated by a non-Abelian dark gauge group. Alternatively, the decaying operator can arise as a Planck suppressed correction in a model with an Abelian discrete symmetry and vector-like states at an intermediate scale that are responsible for generating lepton Yukawa couplings. A flavor-nonconserving dark matter decay is also considered in the case of fermionic dark matter. Assuming a general Dirac structure for the four-fermion contact interactions of interest, the cosmic-ray electron and positron spectra were studied. We show that good fits to the current data can be obtained for both charged-leptonflavor- conserving and flavor-violating decay channels. Motivated by a possible excess of gamma rays in the galactic center, we constructed a supersymmetric leptophilic higgs model to explain the excess. Finally, we consider an improvement on dark matter collider searches using the Razor analysis, which was originally utilized for supersymmetry searches by the CMS collaboration.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Probing the Sustainable Reduction of CO 2 , N 2 and NO 3 to Fuels and Chemicals using Non-Traditional Porphyrinoid Catalysts

For the last several decades, numerous strategies have been proposed to be able to interconvert electricity and commodity fuels for transportation and other applications. Even as solar and wind energy become more widely available, these renewable energy sources are not always available where the population is most dense or during peak times of energy demand. One plausible solution to the issue of electricity storage and transport is to use electricity to drive the formation of high-energy compounds and chemical fuels. As a result, the electrochemical conversion of CO 2 into chemical fuels has received major attention as a multi-pronged approach for electricity coversion, storage, and transport. Similar strategies are also attractive for conversion of N 2 and NO x into value added compounds such as ammonia. Metalloporphyrin and metallocorrole complexes are comprised of aromatic tetrapyrrole scaffolds and have been extensively studied as homogeneous catalysts for critical catalytic processes like the electrochemical CO 2 reduction reaction (eCO 2 RR) to generate CO as feedstock for the Fischer–Tropsch process to generate a variety of hydrocarbons as chemical fuels. Despite their significance and impact, efficiently driving such catalytic reduction processes is challenging for multiple reasons. Such processes require multiple-electron transfer events, as opposed to single-electron redox chemistry that forms high-energy singly-reduced intermediates. In addition, these electron transfer events must be coupled to proton-transfer steps and avoid application of high overpotentials where proton (H + ) reduction to generate H 2 (as well as other side-reactions) can lower the selectivity and energy efficiency of the eCO 2 RR process. Certain Fe(III) aromatic tetrapyrroles (e.g., porphyrins and corroles) have been reported to overcome these challenges, but are often difficult to synthesize and modify, and have a tendency to support single-electron redox chemistry at the metal as opposed to multielectron redox involving the ligand and metal in concert. Other families of tetrapyrroles in which all four meso-carbons are reduced (i.e., sp 3 -hybridized) are also known in the literature. These non-aromatic tetrapyrroles are known as porphyrinogens and support multi-electron redox chemistry which has been elaborated by several groups, prompting researchers to consider whether these scaffolds may improve the kinetics and efficiencies of multi-electron steps attendant to activation of thermodynamically stable small-molecule substrates such as CO 2 , N 2 , NO 3 − , and NO 2 − . Although porphyrinogens support multi-electron redox properties, the four sp 3 -hybridized meso-carbons inherent to the tetrapyrrole core completely disrupt π-conjugation between pyrrolic units, which compromises the photochemical properties of porphyrinogens in comparison to that of traditional porphyrinoids. Moreover, the highly reducing nature of porphyrinogens predisposes these platforms to extreme air and water sensitivity. Accordingly, such metalated porphyrinogens are often pyrophoric and/or incompatible with many common organic solvents (CH 2 Cl 2 , CHCl 3 , CH 3 CN, EtOAc, etc.). Hence, reports of efficient small-molecule activation or catalysis supported by porphyrinogens have been limited. To overcome the instability of porphyrinogens while retaining the scaffold’s attractive multi-electron redox properties, we have directed attention to establishing less-well studied groups of non-aromatic tetrapyrroles (i.e., phlorins, biladienes, and isocorroles). These non-traditional tetrapyrroles each contain just a single sp 3 -hybridized meso-carbon, which ablates the platforms aromaticity but still provides an extended π-framework. In addition to developing innovative platforms that may be used to sustainably generate value-added chemicals, fuels, and ammonia via either photo- or electrocatalytic approaches our work also has significantly broadened our understanding of how to prepare and modulate the properties of non-aromatic tetrapyrroles for other applications. Our efforts entailed a synergistic partnership and active collaborations with Drs. David C. Grills and Mehmed Z. Ertem (both of Brookhaven National Lab) to better characterize isocorroles (and related non-aromatic tetrapyrroles) using a variety of advanced spectroscopic and theoretical methods. Our combined efforts have shown that the combination of properties that isocorroles (and related tetrapyrroles) provide results in good chemical stability paired with unique redox and photochemical characteristics that are not typically supported by simple and/or unadorned aromatic tetrapyrroles. Beside redox chemistry, the photochemistry of isocorroles and other non-aromatic tetrapyrroles containing one sp 3 -hybridized meso-carbon is also appealing due to their absorption in the long-visible to near-IR regions, which are essential for photocatalysis and related applications that benefit from direct excitation at these wavelengths. The results reported vastly improve our understanding of non-aromatic tetrapyrrole synthesis, properties and utility for activation of small molecule substrates such as O 2 and CO 2 in the presence of weak cationic organic acids.

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

Tunable Geometries in Sparse Clifford Circuits

We investigate the emergence of different effective geometries in stochastic Clifford circuits with sparse coupling. By changing the probability distribution for choosing two-site gates as a function of distance, we generate sparse interactions that either decay or grow with distance as a function of a single tunable parameter. Tuning this parameter reveals three distinct regimes of geometry for the spreading of correlations and growth of entanglement in the system. We observe linear geometry for short-range interactions, treelike geometry on a sparse coupling graph for long-range interactions, and an intermediate fast scrambling regime at the crossover point between the linear and treelike geometries. This transition in geometry is revealed in calculations of the subsystem entanglement entropy and tripartite mutual information. We also study emergent lightcones that govern these effective geometries by teleporting a single qubit of information from an input qubit to an output qubit. These tools help to analyze distinct geometries arising in dynamics and correlation spreading in quantum many-body systems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Subphotospheric Emission from Short Gamma-Ray Bursts: Protons Mold the Multimessenger Signals

Abstract The origin of the observed Band-like photon spectrum in short gamma-ray bursts (sGRBs) is a long-standing mystery. We carry out the first general relativistic magnetohydrodynamic simulation of an sGRB jet with initial magnetizationσ 0 = 150 in dynamical ejecta from a binary merger. From this simulation, we identify regions along the jet of efficient energy dissipation due to magnetic reconnection and collisionless subshocks. Taking into account electron and proton acceleration processes, we solve for the first time the coupled transport equations for photons, electrons, protons, neutrinos, and intermediate particle species up to close to the photosphere (i.e., up to 1 × 10 12 cm), accounting for all relevant radiative and cooling processes. We find that the subphotospheric multimessenger signals carry strong signatures of the hadronic interactions and their resulting particle cascades. Importantly, the spectral energy distribution of photons is significantly distorted with respect to the Wien one, commonly assumed below the photosphere. Our findings suggest that the bulk of the nonthermal photon spectrum observed in sGRBs can stem from hadronic processes occurring below the photosphere and previously neglected, with an accompanying energy flux of neutrinos peaking in the GeV energy range.

Astronomy & Astrophysics↗
NASA NTRS1974

Device for recording the 20 Hz - 200 KHz sound frequency spectrum using teletransmission

The device described consists of two distinct parts: (1) The sound pickup system consisting of the wide-frequency band condenser microphone which contains in the same assembly the frequency-modulated oscillator and the output stage. Being transistorized and small, this system can be easily moved, so that sounds can be picked up even in places that are difficult to reach with larger devices. (2) The receiving and recording part is separate and can be at a great distance from the sound pickup system. This part contains a 72 MHz input stage, a frequency changer that gives an intermediate frequency of 30 MHz and a multichannel analyzer coupled to an oscilloscope and a recorder.

Baciu, I.↗
DOE OSTI2011

Scalar perturbations in conformal rolling scenario with intermediate stage

Scalar cosmological perturbations with nearly flat power spectrum may originate from perturbations of the phase of a scalar field conformally coupled to gravity and rolling down negative quartic potential. We consider a version of this scenario whose specific property is a long intermediate stage between the end of conformal rolling and horizon exit of the phase perturbations. Such a stage is natural, e.g., in cosmologies with ekpyrosis or genesis. Its existence results in small negative scalar tilt, statistical anisotropy of all even multipoles starting from quardupole of general structure (in contrast to the usually discussed single quadrupole of special type) and non-Gaussianity of a peculiar form.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Tandem In 2 O 3 -Pt/Al 2 O 3 catalyst for coupling of propane dehydrogenation to selective H 2 combustion

Tandem catalysis couples multiple reactions and promises to improve chemical processing, but precise spatiotemporal control over reactive intermediates remains elusive. We used atomic layer deposition to grow In 2 O 3 over Pt/Al 2 O 3 , and this nanostructure kinetically couples the domains through surface hydrogen atom transfer, resulting in propane dehydrogenation (PDH) to propylene by platinum, then selective hydrogen combustion by In 2 O 3 , without excessive hydrocarbon combustion. Other nanostructures, including platinum on In 2 O 3 or platinum mixed with In 2 O 3 , favor propane combustion because they cannot organize the reactions sequentially. The net effect is rapid and stable oxidative dehydrogenation of propane at high per-pass yields exceeding the PDH equilibrium. Tandem catalysis using this nanoscale overcoating geometry is validated as an opportunity for highly selective catalytic performance in a grand challenge reaction.

Yan, Huan↗
DOE OSTI2015

On uniform plasma generation for the large area plasma processing in intermediate pressures

Radial plasma discharge characteristics in the range of 450 mm were studied in a dual inductively coupled plasma (ICP) source, which consisted of a helical ICP and the side type ferrite ICPs. Since the energy relaxation length is shorter than the distance between each of the ferrite ICPs in an intermediate pressure (600 mTorr), local difference in the plasma ignition along the antenna position were observed. In addition, large voltage drop in the discharge of the ferrite ICPs causes an increase in the displacement current to the plasma, and separate discharge mode (E and H mode) according to the antenna position was observed. This results in non-uniform plasma distribution. For the improvement in the discharge of the ferrite ICPs, a capacitor which is placed between the ends of antenna and the ground is adjusted to minimize the displacement current to the plasma. As a result, coincident transitions from E to H mode were observed along the antenna position, and radially concave density profile (edge focused) was measured. For the uniform density distribution, a helical ICP, which located at the center of the discharge chamber, was simultaneously discharged with the ferrite ICPs. Due to the plasma potential variation through the simultaneous discharge of helical ICP and ferrite ICPs, uniform radial distribution in both plasma density and electron temperature are achieved.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Controlled calculation of the thermal conductivity for a spinon Fermi surface coupled to a U(1) gauge field

Motivated by recent transport measurements on the candidate spin-liquid phase of the organic triangular lattice insulator EtMe{sub 3}Sb[Pd(dmit){sub 2}]{sub 2}, we perform a controlled calculation of the thermal conductivity at intermediate temperatures in a spin liquid system where a spinon Fermi surface is coupled to a U(1) gauge field. The present computation builds upon the double expansion approach developed by Mross et al. (2010) for small ϵ=z{sub b}−2 (where z{sub b} is the dynamical critical exponent of the gauge field) and large number of fermionic species N. Using the so-called memory matrix formalism that most crucially does not assume the existence of well-defined quasiparticles at low energies in the system, we calculate the temperature dependence of the thermal conductivity κ of this model due to non-critical Umklapp scattering of the spinons for a finite N and small ϵ. Then we discuss the physical implications of such theoretical result in connection with the experimental data available in the literature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2011

Moment coupling in the interaction of atoms and their ions with a 3d-electron shell

The moment coupling of an interacting ion and an atom with a 3d-electron shell is analyzed for the ground state of identical atoms and ions where resonant charge exchange proceeds with transition of a 4s-electron. The interaction of the ion charge with the atom quadrupole moment is important for this system along with the exchange interactions and spin-orbit interactions inside an isolated atom and an ion. The quadrupole moment for 3d-atoms in the ground states is evaluated. The hierarchy of interactions in a molecular ion is analyzed depending on ion-atom distances and is compared with the standard Hund scheme. The resonant charge exchange proceeds effectively at separations corresponding to an intermediate case between cases 'a' and 'c' of the Hund coupling scheme.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2011

Dephasing of strong coupling in the non-linear regime

We study the effect of pure dephasing on the strong-coupling of a two-level system (typically, a quantum dot) with the single mode of a microcavity. Whereas dephasing merely broadens the line in the linear regime, it results in a new spectral shape when transitions between higher manifolds of the Jaynes-Cummings ladder are involved, namely, a triplet, that we show does not imply weak-coupling. Higher excitation brings the system into lasing. Description of this intermediate triplet allows to demonstrate quantum nonlinearities even in noisy systems and to measure the magnitude of dephasing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRSDate not supplied

Intermediate Temperature Ceramic Heat Pipe Modeling and Optimization

The intermediate temperature regime of heat pipes, 450-700 K, has not been well characterized due in part to the corrosive nature of many of the working fluids, as well as the poor performance in many conventional metal envelope systems. Spacecraft nuclear electric propulsion, as well as other emerging technologies, can benefit from heat pipes with optimal performance in this intermediate regime. In this work, we have explored halide working fluids coupled with aluminum nitride shells to operate at 500-600 K and interface with a nuclear electric propulsion system. The shells have been additively manufactured and tested to ensure compatibility with the halides. Specifically, AlBr 3 , AlCl 3 , FeCl 3 , and SbBr 3 were selected owing to their higher performance and comparatively safe handling characteristics compared to other intermediate temperature working fluids. The additive manufacturing process enables highly customizable designs that integrate the heat pipe and radiator fin together, optimized for each fluid. We have evaluated the performance limits of such a heat pipe design in order to establish the feasibility of AlBr 3 in particular, and present design that achieves an areal density of 5.2 kg/m 2 and mass per unit heat performance of 0.71 kg/kW. Analysis is ongoing for all working fluids.

thermal management↗
DOE OSTI2026

Modern insights into the mechanisms of neptunium oxalate decomposition

Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗
DOE OSTI2026

Low-Temperature Non-Oxidative Coupling of Methane on Atomically Dispersed Titanium–Aluminum–Boron Nanopowder

Nonoxidative coupling of methane represents a long-standing challenge in heterogeneous catalysis, as it requires activation of the carbon–hydrogen (C–H) bond, controlled carbon–carbon (C–C) bond formation, and effective hydrogen management without relying on oxidants. Here, we report a low-temperature C–H activation and nonoxidative C–C coupling of methane over atomically dispersed titanium–aluminum–boron nanopowder (Ti–Al–B NP) utilizing a catalytic microreactor coupled to synchrotron single-photon photoionization reflectron time-of-flight mass spectrometry. The soft-ionization, in situ probing method detects the nascent reaction products and radical intermediates under operando conditions, including methyl radical, C2 hydrocarbons, and molecular hydrogen. Methane activation is initiated at 800 K, approximately 700 K below the gas-phase decomposition threshold, leading predominantly to ethylene formation with selectivity reaching up to 78% among the C–C coupled products. Electronic structure calculations on model Ti–Al–B clusters elucidate a cooperative catalytic mechanism in which titanium enables methane adsorption and C–H activation, boron acts as a reversible hydrogen reservoir, and aluminum stabilizes methylene intermediates, thereby facilitating selective C–C coupling and dehydrogenation. These findings establish a distinct catalyst architecture for nonoxidative methane coupling based on earth abundant elements alternative to expensive platinum and other noble metal-containing conventional catalysts and provide molecular-level design principles for controlling dehydrogenation and subsequent C–C bond formation in challenging light alkane conversions.

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

Synthesis of a biofuel target through conventional organic chemistry

In this work, the biofuel target compound 2-ethyl-5,5-dimethylcyclopenta-1,3-diene (1) and its exo isomers (9a and 9b), were successfully synthesized via two different pathways from the common intermediate 4,4-dimethylcyclopent-2-ene-1-one (2). The first pathway produced the endocyclic product as a pure isomer via a triflate intermediate obtained from the ketone 2 in 60% yield, followed by copper catalyzed coupling with ethyl magnesium bromide in 63% yield. The second pathway employed a Grignard reaction with ketone 2, which generated an alcohol that was immediately subjected to mild acid catalyzed elimination upon workup of the previous step to yield a primarily a mixture of exo diastereomers 9a and 9b in 77% yield. These targets had their fuel properties characterized in a separate study.

Biofuel↗