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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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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Optimal system size for complex dynamics in random neural networks near criticality

In this article, we consider a model of dynamical agents coupled through a random connectivity matrix, as introduced by Sompolinsky et al. [Phys. Rev. Lett. 61(3), 259–262 (1988)] in the context of random neural networks. When system size is infinite, it is known that increasing the disorder parameter induces a phase transition leading to chaotic dynamics. We observe and investigate here a novel phenomenon in the sub-critical regime for finite size systems: the probability of observing complex dynamics is maximal for an intermediate system size when the disorder is close enough to criticality. We give a more general explanation of this type of system size resonance in the framework of extreme values theory for eigenvalues of random matrices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Broken-Symmetry Density Functional Theory Analysis of the Ω Intermediate in Radical S -Adenosyl- l -methionine Enzymes: Evidence for a Near-Attack Conformer over an Organometallic Species

Radical S-adenosyl-L-methionine (SAM) enzymes are found in all domains of life and catalyze a wide range of biochemical reactions. Recently, an organometallic intermediate, Ω, has been experimentally implicated in the 5'-deoxyadenosyl radical generation mechanism of the radical SAM superfamily. In this work, we employ broken-symmetry density functional theory to evaluate several structural models of Ω. The results show that the calculated hyperfine coupling constants (HFCCs) for the proposed organometallic structure of Ω are inconsistent with the experiment. In contrast, a near-attack conformer of SAM bound to the catalytic [4Fe–4S] cluster, in which the distance between the unique iron and SAM sulfur is ~3 Å, yields HFCCs that are all within 1 MHz of the experimental values. Furthermore, these results clarify the structure of the ubiquitous Ω intermediate and suggest a paradigm shift reversal regarding the mechanism of SAM cleavage by members of the radical SAM superfamily.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Phase transformations, microstructural refinement and defect evolution mechanisms in Al-Si alloys under non-hydrostatic diamond anvil cell compression

Non-hydrostatic compression of materials using a diamond anvil cell (DAC) can transform equilibrium microstructure of an alloy to novel, potentially metastable states. In this study, in situ synchrotron X-ray diffraction (XRD) during compression up to 24 GPa and subsequent ex situ, high resolution analytical electron microscopy (AEM) after decompression of an Al-Si alloy provided insight into the crystallographic changes during the compression as well as microstructural refinement, and defect structures caused by such a high pressure compression-decompression process. Pressure resolved in-situ synchrotron XRD was used to detail the phase transformation pathway of the eutectic Si phase in Al-Si alloy, from Si-I → Si-XI → Si-V during compression, and a final transformation predominantly to Si-III after decompression. Using scanning and transmission electron microscopy (S/TEM), site specific analysis of the alloy immediately underneath the anvil contact surface demonstrated a highly complex microstructure. A narrow region of thick amorphous Al oxide interspersed with nanocrystalline grains was found at the top surface. Underneath this Al oxide, while the majority the eutectic Si was transformed into highly-deformed, polycrystalline (PC) Si-III, a complex intermediate layer was discovered at the interface between Al and Si, comprised of a small fraction of Al nanocrystals and a majority of nanocrystalline Si-I. This combination of pressure resolved in-situ synchrotron XRD coupled with subsequent high resolution, electron microscopy resolved the phase transformation as well as non-equilibrium microstructures in a metallic alloy induced by a non-hydrostatic high pressure compression followed by decompression.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Low-Coordinated Pd Catalysts Supported on Zn 1 Zr 1 O x Composite Oxides for Selective Methanol Steam Reforming

Highly dispersed palladium on nanoscale Zn 1 Zr 1 O x mixed oxides was prepared by incipient wetness impregnation. H 2 pretreatment tuned the structure of the catalysts and, hence the catalytic performance in the steam reforming of methanol. Based on catalyst evaluation by XRD, XPS and EXAFS/XANES, it is found that high reduction temperature (400 °C) leads to the formation of PdZn β alloy, which breaks the Pd-Pd bonds in the metallic Pd phase and forms low-coordinated Pd species in the domain of the metal oxides. These low-coordinated Pd species are responsible for the exclusive selectivity to CO 2 as the carbon product. Methyl formate as the reaction intermediate was detected on Pd/Zn 1 Zr 1 O x -R400 catalyst by in situ methanol-DRIFTS and methanol-TPSR, proving the methanol dehydrogenation and coupling reaction pathway on the low-coordinated Pd active sites. The incorporation of ZrO 2 facilitates the dispersion of ZnO and Pd species and stabilizes Pd species against growth, with better stability than monometallic palladium. This work effectively shows how to prepare active and selective Pd catalysts for dehydrogenation and steam reformimg of methanol not suffering from the typical poor selectivity of metallic palladium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator

To explore the possibility of a fullerene acting as an electron and/or singlet energy relay between a donor chromophore and an acceptor, a triad consisting of a fullerene (C 60 ) covalently linked to both a porphyrin energy and electron donor (P) and a β-tetracyanoporphyrin energy and electron acceptor (CyP) was synthesized. Steady state and time-resolved spectroscopic investigations show that the porphyrin first excited singlet state donates singlet excitation and an electron to the fullerene and also donates singlet excitation to the CyP. All three processes differ in rate constant by factors of ≤1.3, and all are much faster than the decay of 1 P–C 60 –CyP by unichromophoric processes. The fullerene excited state accepts an electron from P and donates singlet excitation energy to CyP. The P •+ –C 60 •– –CyP charge-separated state transfers an electron to CyP to produce a final P •+ –C 60 –CyP •– state. The same state is formed from P–C 60 – 1 CyP. Overall, the final charge-separated state is formed with a quantum yield of 85% in benzonitrile, and has a lifetime of 350 ps. Rate constants for formation and quantum yields of all intermediate states were estimated from results for the triad and several model compounds. Interestingly, the intermediate P •+ –C 60 •– –CyP charge-separated state has a lifetime of 660 ps. It is longer lived than the final state in spite of stronger coupling of the radical ions. Moreover, this is ascribed to the fact that recombination lies far into the inverted region of the Marcus rate constant vs thermodynamic driving force relationship.

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

Additive Molar Volumes in Amorphous Ca/Sr Carbonate Solid Solutions

The development of predictive models of minor element incorporation in crystalline carbonate end products requires an understanding of the fundamental controls on metastable intermediate phase composition. In this study, we used small-angle X-ray scattering (SAXS), X-ray pair distribution function (PDF), thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry (ICP-MS), and transmission electron microscopy (TEM) to determine the composition-dependent density of an amorphous calcium–strontium carbonate (ACSC) solid solution. The amorphous calcium carbonate (ACC) and strontium carbonate (ASC) measured densities were ρ ACC = 2.19 ± 0.04 g/cm 3 and ρ ASC = 2.97 ± 0.05 g/cm 3 . Throughout our work, the experiments showed a dependence of the water content of the amorphous solid solution on the Sr mole fraction. An equation that relates the molar volume to the average cation radius, the carbonate ion radius, and the water volume was parameterized for hydrated crystalline carbonates and predicted well the molar volume of the ACSC solid solution. This finding indicates that, as for hydrated crystalline carbonates, the molar volumes of amorphous carbonates are additive and that water is a structural component of ACSC. Ab initio molecular dynamics (AIMD) simulations of the ACSC solid solutions showed strong linear correlations between calculated molar volumes and Sr and H 2 O contents, thus supporting the experimental results. In conclusion, our findings highlight the need to consider the full CaCO 3 –MeCO 3 –H 2 O ternary when quantifying metal cation incorporation in ACC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Management of light absorption in extraordinary optical transmission based ultra-thin-film tandem solar cells

Although ultra-thin-film solar cells can be attractive in reducing the cost, they suffer from low absorption as the thickness of the active layer is usually much smaller than the wavelength of incident light. Different nano-photonic techniques, including plasmonic structures, are being explored to increase the light absorption in ultra-thin-film solar cells. More than one layer of active materials with different energy bandgaps can be used in tandem to increase the light absorption as well. However, due to different amount of light absorption in different active layers, photo-generated currents in different active layers will not be the same. The current mismatch between the tandem layers makes them ineffective in increasing the efficiency. In this work, we investigate the light absorption properties of tandem solar cells with two ultra-thin active layers working as two subcells and a metal layer with periodically perforated holes in-between the two subcells. While the metal layer helps to overcome the current mismatch, the periodic holes increase the absorption of incident light by helping extraordinary optical transmission of the incident light from the top to the bottom subcell, and by coupling the incident light to plasmonic and photonic modes within ultra-thin active layers. We extensively study the effects of the geometry of holes in the intermediate metal layer on the light absorption properties of tandem solar cells with ultra-thin active layers. We also study how different metals in the intermediate layer affect the light absorption; how the geometry of holes in the intermediate layer affects the absorption when the active layer materials are changed; and how the intermediate metal layer affects the collection of photo-generated electron-hole pairs at the terminals. We find that in a solar cell with 6,6-phenyl C61-butyric acid methyl ester top subcell and copper indium gallium selenide bottom subcell, if the periodic holes in the metal layer are square or polygon, total absorption remains approximately the same. However, the total absorption suffers significantly if the holes are triangle. The transmission spectra of incident light into the bottom subcell, and hence the absorption, change significantly for square and circle holes if the active materials change to cadmium selenide (CdSe) and cadmium telluride (CdTe) in the top and bottom subcells, respectively. Although the intermediate metal layer may induce electron-hole pair recombination due to surface defects, the short-circuit current density of an ultra-thin plasmonic solar cell with an intermediate metal layer with two-dimensional hole array is >9% of that of a structure without the intermediate metal layer.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Imitation of spin density wave order in Cu 3 Nb 2 O 8

Spin density waves, based on modulated local moments, are usually associated with metallic materials, but have recently been reported in insulators which display coupled magnetic and structural order parameters. Here, we discuss one such example, the multiferroic Cu 3 Nb 2 O 8 , which is reported to undergo two magnetic phase transitions, first to an unknown antiferromagnetic phase at $T_N$ ≈ 26.5 K , and then to a helicoidal structure coupled to an electric polarization below $T_2$ ≈ 24 K which breaks the crystallographic inversion symmetry. By analogy with other complex oxides, one might naturally expect this intermediate phase to be a spin density wave phase. We apply spherical polarimetry to confirm the low-temperature magnetic structure, yet only observe a single magnetic phase transition to helicoidal order. We argue that the reported unknown phase actually supports an imitation spin density wave which originates from a decoupling of the components of the magnetic order parameter, as allowed by symmetry and driven by thermal fluctuations. This provides a mechanism for the magnetic, but not nuclear, structure to break inversion symmetry thereby creating an intermediate phase in the proximity of $T_N$ which imitates a spin density wave. As the temperature is reduced, this intermediate structure destabilizes the crystal such that a structural chirality is induced, as reflected by the emergence of the electric polarization, and the imitation spin density wave relaxes into a generic helicoid. This scenario in which critical fluctuations allow the magnetic structure to break inversion symmetry while the crystal structure remains centrosymmetric might be relevant to other complex multiferroics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

New observables for $CP$ violation in Higgs decays

Current experimental data on the 125 GeV Higgs boson still allow room for large $CP$ violation. The observables usually considered in this context are triple product asymmetries, which require an input of four visible particles after imposing momentum conservation. Here, we point out a new class of $CP$ -violating observables in Higgs physics which require only three reconstructed momenta. They may arise if the process involves an interference of amplitudes with different intermediate particles, which provide distinct “strong phases” in the form of the Breit-Wigner widths, in addition to possible “weak phases” that arise from $CP$ -violating couplings of the Higgs in the Lagrangian. As an example, we propose a forward-backward asymmetry of the charged lepton in the three-body Higgs decay, h → ℓ $-$ ℓ + γ , as a probe for $CP$ -violating Higgs couplings to Zγ and γγ pairs. In conclusion, we also discuss other processes exhibiting this type of $CP$ violation.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

Fractionation and catalytic upgrading of bio-oil

The goal was to develop a biomass conversion process that optimizes fractionation and conversion to maximize Carbon efficiency and Hydrogen consumption to obtain drop-in fuels. Selective fractionation of raw biomass was obtained via multi-stage thermal fractionation to produce different streams that are enriched in a particular chemical family (acids, furanics or phenolics). These streams were later catalytically upgraded in both liquid and vapor phase to perform C-C bond formation and hydrodeoxygenation. Among various upgrading strategies investigated we have identified an effective path in which cyclopentanone is a crucial intermediate that can be derived from furfural and other furanics obtained in high concentrations from this thermal staged process. Cyclopentanone is a very versatile molecule, which can couple with itself to product high quality jet-fuel, or couple with phenolic or furanics to create long chain molecules. These (mono-oxygenated) compounds in the correct molecular weight fuel range can be hydrotreated to direct drop-in fuels. Interestingly, we have found that the conversion of furfural to cyclopentanone is not affected by the presence of acetic acid, and, more interestingly, it is enhanced by the presence of water. These are very significant findings, since water and acetic acid are always present in all streams from the primary conversion stage. These results have allowed to complete detailed life-cycle assessment and techno-economic analysis that have been back-fed to the experimentalists to refine the catalyst selection and process operations with the objective of maximizing C efficiency at minimum H utilization. These combined investigations have opened the possibility of an economically and technologically effective process that could result in commercial fuels produced from renewable sources at a cost that might be competitive with fossil fuels.

09 BIOMASS FUELS↗
NASA NTRS1996

Lateral-Directional Eigenvector Flying Qualities Guidelines for High Performance Aircraft

This report presents the development of lateral-directional flying qualities guidelines with application to eigenspace (eigenstructure) assignment methods. These guidelines will assist designers in choosing eigenvectors to achieve desired closed-loop flying qualities or performing trade-offs between flying qualities and other important design requirements, such as achieving realizable gain magnitudes or desired system robustness. This has been accomplished by developing relationships between the system's eigenvectors and the roll rate and sideslip transfer functions. Using these relationships, along with constraints imposed by system dynamics, key eigenvector elements are identified and guidelines for choosing values of these elements to yield desirable flying qualities have been developed. Two guidelines are developed - one for low roll-to-sideslip ratio and one for moderate-to-high roll-to-sideslip ratio. These flying qualities guidelines are based upon the Military Standard lateral-directional coupling criteria for high performance aircraft - the roll rate oscillation criteria and the sideslip excursion criteria. Example guidelines are generated for a moderate-to-large, an intermediate, and low value of roll-to-sideslip ratio.

Davidson, John B.↗
DOE OSTI2014

Reversal bending fatigue testing

Embodiments for apparatuses for testing reversal bending fatigue in an elongated beam are disclosed. Embodiments are configured to be coupled to first and second end portions of the beam and to apply a bending moment to the beam and create a pure bending condition in an intermediate portion of the beam. Embodiments are further configured to cyclically alternate the direction of the bending moment applied to the beam such that the intermediate portion of the beam cyclically bends in opposite directions in a pure bending condition.

42 ENGINEERING↗
DOE OSTI2021

An Iron(IV)–Oxo Intermediate Initiating l-Arginine Oxidation but Not Ethylene Production by the 2-Oxoglutarate-Dependent Oxygenase, Ethylene-Forming Enzyme

Ethylene-forming enzyme (EFE) is an ambifunctional iron(II)- and 2-oxoglutarate-dependent (Fe/2OG) oxygenase. In its major (EF) reaction, it converts carbons 1, 2, and 5 of 2OG to CO 2 and carbons 3 and 4 to ethylene, a four-electron oxidation drastically different from the simpler decarboxylation of 2OG to succinate mediated by all other Fe/2OG enzymes. EFE also catalyzes a minor reaction, in which the normal decarboxylation is coupled to oxidation of L-arginine (a required activator for the EF pathway), resulting in its conversion to L-glutamate semialdehyde and guanidine. Here we show that, consistent with precedent, the L-Arg-oxidation (RO) pathway proceeds via an iron(IV)-oxo (ferryl) intermediate. Use of 5,5-[ 2 H 2 ]-L-Arg slows decay of the ferryl complex by >16-fold, implying that RO is initiated by hydrogen-atom transfer (HAT) from C5. That this large substrate deuterium kinetic isotope effect has no impact on the EF:RO partition ratio implies that the same ferryl intermediate cannot be on the EF pathway; the pathways must diverge earlier. Consistent with this conclusion, the variant enzyme bearing the Asp191Glu ligand substitution accumulates ~ four times as much of the ferryl complex as the wild-type enzyme and exhibits a ~ 40-fold diminished EF:RO partition ratio. Here, the selective detriment of this nearly conservative substitution to the EF pathway implies that it has unusually stringent stereoelectronic requirements. An active-site, like-charge guanidium pair, which involves the L-Arg substrate/activator and is unique to EFE among four crystallographically characterized L-Arg modifying Fe/2OG oxygenases, may serve to selectively stabilize the transition state leading to the unique EF branch.

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

Three-body DD{pi} dynamics for the X(3872)

We investigate the role played by the three-body DD{pi} dynamics on the near-threshold resonance X(3872) charmonium state, which is assumed to be formed by nonperturbative DD{sup *} dynamics. It is demonstrated that, as compared to the naive static-pions approximation, the imaginary parts that originate from the inclusion of dynamical pions reduce substantially the width from the DD{pi} intermediate state. In particular, for a resonance peaked at 0.5 MeV below the D{sup 0}D{sup *0} threshold, this contribution to the width is reduced by about a factor of 2, and the effect of the pion dynamics on the width grows as long as the resonance is shifted towards the D{sup 0}D{sup 0{pi}0} threshold. Although the physical width of the X is dominated by inelastic channels, our finding should still be of importance for the X line shapes in the DD{pi} channel below DD{sup *} threshold. For example, in the scattering length approximation, the imaginary part of the scattering length includes effects of all the pion dynamics and does not only stem from the D{sup *} width. Meanwhile, we find that another important quantity for the X phenomenology, the residue at the X pole, is weakly sensitive to dynamical pions. In particular, we find that the binding energy dependence of this quantity from the full calculation is close to that found from a model with pointlike DD{sup *} interactions only, consistent with earlier claims. Coupled-channel effects (inclusion of the charged DD{sup *} channel) turn out to have a moderate impact on the results.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2017

Single field double inflation and primordial black holes

Within the framework of scalar-tensor theories, we study the conditions that allow single field inflation dynamics on small cosmological scales to significantly differ from that of the large scales probed by the observations of cosmic microwave background. The resulting single field double inflation scenario is characterised by two consequent inflation eras, usually separated by a period where the slow-roll approximation fails. At large field values the dynamics of the inflaton is dominated by the interplay between its non-minimal coupling to gravity and the radiative corrections to the inflaton self-coupling. For small field values the potential is, instead, dominated by a polynomial that results in a hilltop inflation. Without relying on the slow-roll approximation, which is invalidated by the appearance of the intermediate stage, we propose a concrete model that matches the current measurements of inflationary observables and employs the freedom granted by the framework on small cosmological scales to give rise to a sizeable population of primordial black holes generated by large curvature fluctuations. We find that these features generally require a potential with a local minimum. We show that the associated primordial black hole mass function is only approximately lognormal.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

In situ x-ray absorption investigations of a heterogenized molecular catalyst and its interaction with a carbon nanotube support

A highly active heterogenized molecular CO 2 reduction catalyst on a conductive carbon support is investigated to identify if its improved catalytic activity can be attributed to strong electronic interactions between catalyst and support. The molecular structure and electronic character of a [Re +1 (tBu-bpy)(CO) 3 Cl] (tBu-bpy = 4,4'-tert-butyl-2,2'-bipyridine) catalyst deposited on multiwalled carbon nanotubes are characterized using Re L 3 -edge x-ray absorption spectroscopy under electrochemical conditions and compared to the homogeneous catalyst. The Re oxidation state is characterized from the near-edge absorption region, while structural changes of the catalyst are assessed from the extended x-ray absorption fine structure under reducing conditions. Chloride ligand dissociation and a Re-centered reduction are both observed under applied reducing potential. The results confirm weak coupling of [Re(tBu-bpy)(CO) 3 Cl] with the support, since the supported catalyst exhibits the same oxidation changes as the homogeneous case. However, these results do not preclude strong interactions between a reduced catalyst intermediate and the support, preliminarily investigated here using quantum mechanical calculations. Thus, our results suggest that complicated linkage schemes and strong electronic interactions with the initial catalyst species are not required to improve the activity of heterogenized molecular catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗