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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Unveiling the Multielectron Acceptor Properties of π-Expanded Pyracylene: Reversible Boat to Chair Conversion

In this work, the chemical reduction of a hybrid pyracylene-hexa-peri-hexabenzocoronene (HPH) nanographene was investigated with different alkali metals (Na, K, Rb) to reveal its remarkable multielectron acceptor abilities. The UV–vis and 1 H NMR spectroscopy monitoring of the stepwise reduction reactions supports the existence of all intermediate reduction states up to the hexaanion for HPH. Tuning the experimental conditions enabled the synthesis of the HPH anions with gradually increasing reduction states (up to –5) isolated with different alkali metal ions as crystalline materials. The single-crystal X-ray diffraction structure analysis demonstrates that the highly negatively charged HPH anions (–4 and –5) exhibit a drastic geometry change from boat-shaped (observed in the neutral parent, mono- and dianions) to a chair conformation, which was proved to be fully reversible by NMR spectroscopy. DFT calculations show that this geometry change is induced by an enhanced interaction between the coordinated metal ions and negatively charged HPH core in the chair conformation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Siderite at lower mantle conditions and the effects of the pressure-induced spin-pairing transition

Siderite (FeCO{sub 3}) forms a complete solid solution with magnesite (MgCO{sub 3}), the most likely candidate for a mantle carbonate. Our experiments with natural siderite reveal spin pairing of d-orbital electrons of Fe{sup 2+} at 43 GPa, as evidenced by a sharp volume collapse of about 10%. The initially colorless crystals assume an intense green color after the transition, which progressively turns to red above 60 GPa. We present clear evidence for the instability of an intermediate spin state in siderite at ambient temperature. At the transition pressure, domains of high and low spin siderite coexist. The unit cell volume difference between magnesite and siderite is significantly decreased by the spin transition, enhancing the solubility between the two calcite-type minerals. A siderite component in magnesite at lower mantle pressure would significantly increase its density and slightly increase the carbonate bulk modulus.

58 GEOSCIENCES↗
DOE OSTI2019

Directing isomerization reactions of cumulenes with electric fields

Electric fields have been proposed as having a distinct ability to catalyze chemical reactions through the stabilization of polar or ionic intermediate transition states. Although field-assisted catalysis is being researched, the ability to catalyze reactions in solution using electric fields remains elusive and the understanding of mechanisms of such catalysis is sparse. Here we show that an electric field can catalyze the cis-to-trans isomerization of [3]cumulene derivatives in solution, in a scanning tunneling microscope. We further show that the external electric field can alter the thermodynamics inhibiting the trans-to-cis reverse reaction, endowing the selectivity toward trans isomer. Using density functional theory-based calculations, we find that the applied electric field promotes a zwitterionic resonance form, which ensures a lower energy transition state for the isomerization reaction. The field also stabilizes the trans form, relative to the cis, dictating the cis/trans thermodynamics, driving the equilibrium product exclusively toward the trans.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Encoding multistate charge order and chirality in endotaxial heterostructures

Abstract High-density phase change memory (PCM) storage is proposed for materials with multiple intermediate resistance states, which have been observed in 1 T -TaS 2 due to charge density wave (CDW) phase transitions. However, the metastability responsible for this behavior makes the presence of multistate switching unpredictable in TaS 2 devices. Here, we demonstrate the fabrication of nanothick verti-lateral H -TaS 2 /1 T -TaS 2 heterostructures in which the number of endotaxial metallic H -TaS 2 monolayers dictates the number of resistance transitions in 1 T -TaS 2 lamellae near room temperature. Further, we also observe optically active heterochirality in the CDW superlattice structure, which is modulated in concert with the resistivity steps, and we show how strain engineering can be used to nucleate these polytype conversions. This work positions the principle of endotaxial heterostructures as a promising conceptual framework for reliable, non-volatile, and multi-level switching of structure, chirality, and resistance.

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

Establishing nonlinearity thresholds with ultraintense X-ray pulses

X-ray techniques have evolved over decades to become highly refined tools for a broad range of investigations. Importantly, these approaches rely on X-ray measurements that depend linearly on the number of incident X-ray photons. The advent of X-ray free electron lasers (XFELs) is opening the ability to reach extremely high photon numbers within ultrashort X-ray pulse durations and is leading to a paradigm shift in our ability to explore nonlinear X-ray signals. However, the enormous increase in X-ray peak power is a double-edged sword with new and exciting methods being developed but at the same time well-established techniques proving unreliable. Consequently, accurate knowledge about the threshold for nonlinear X-ray signals is essential. Here in this paper we report an X-ray spectroscopic study that reveals important details on the thresholds for nonlinear X-ray interactions. By varying both the incident X-ray intensity and photon energy, we establish the regimes at which the simplest nonlinear process, two-photon X-ray absorption (TPA), can be observed. From these measurements we can extract the probability of this process as a function of photon energy and confirm both the nature and sub-femtosecond lifetime of the virtual intermediate electronic state.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Origin of multi-level switching and telegraphic noise in organic nanocomposite memory devices

The origin of negative differential resistance (NDR) and its derivative intermediate resistive states (IRSs) of nanocomposite memory systems have not been clearly analyzed for the past decade. To address this issue, we investigate the current fluctuations of organic nanocomposite memory devices with NDR and the IRSs under various temperature conditions. The 1/f noise scaling behaviors at various temperature conditions in the IRSs and telegraphic noise in NDR indicate the localized current pathways in the organic nanocomposite layers for each IRS. The clearly observed telegraphic noise with a long characteristic time in NDR at low temperature indicates that the localized current pathways for the IRSs are attributed to trapping/de-trapping at the deep trap levels in NDR. This study will be useful for the development and tuning of multi-bit storable organic nanocomposite memory device systems.

42 ENGINEERING↗
DOE OSTI2010

Transformation from molecular to polymeric nitrogen at high pressures and temperatures: In situ x-ray diffraction study

We studied the mechanism of the structural transformation of molecular nitrogen to atomic single-bonded nitrogen with a cubic gauche (cg-N) crystal structure using x-ray diffraction in situ at a pressure of - 140 GPa and temperatures up to 2000 K in a diamond anvil cell. The anvils, with a toroidal shape, allowed us to drastically increase the volume of the sample, reduce the acquisition time of the diffraction pattern, and improve the quality of the Raman spectra. Molecular nitrogen transforms to the cg-N phase through an intermediate disordered state. The Raman spectra are in good agreement with recent theoretical calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Conversion coefficients of the isomeric state in {sup 72}Br

In order to determine the Gamow-Teller strength distribution for the N Z nucleus {sup 72}Kr an experiment was performed with a Total Absorption Gamma Spectrometer. To fully accomplish this task it is crucial to determine the multipolarity of the low energy transitions as the spin-parity of the daughter ground state has been debated. This is done by experimental determination of the conversion coefficients. Preliminary results for the multipolarity and conversion coefficients of the transition connecting the isomeric state at 101 keV with the {sup 72}Br ground state are presented.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2010

N = 28: From Shell to Shapes

New experimental information has been obtained recently on shape coexistence features in {sup 43}S{sub 27} and {sup 44}S{sub 28}. These data confirm that Sulfur isotopes, in the vicinity of N = 28, belong to a region of spherical-deformed shape transition between {sup 48}Ca and {sup 42}Si. In this paper, the onset of collectivity and its impact on the structure of Napprox28 isotones is discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2010

Study of DCX reaction on medium nuclei with Monte-Carlo Shell Model

In this work a method is introduced to calculate the DCX reaction in the framework of Monte-Carlo Shell Model (MCSM). To facilitate the use of Zero-temperature formalism of MCSM, the Double-Isobaric-Analog State (DIAS) is derived from the ground state by using isospin shifting operator. The validity of this method is tested by comparing the MCSM results to those of the SU(3) symmetry case. Application of this method to DCX on {sup 56}Fe and {sup 93}Nb is discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2011

Addition of one and two units of C{sub 2}H to styrene: A theoretical study of the C{sub 10}H{sub 9} and C{sub 12}H{sub 9} systems and implications toward growth of polycyclic aromatic hydrocarbons at low temperatures

Various mechanisms of the formation of naphthalene and its substituted derivatives have been investigated by ab initio G3(MP2,CC)/B3LYP/6-311G** calculations of potential energy surfaces for the reactions of one and two C{sub 2}H additions to styrene combined with RRKM calculations of product branching ratios under single-collision conditions. The results show that for the C{sub 2}H + styrene reaction, the dominant routes are H atom eliminations from the initial adducts; C{sub 2}H addition to the vinyl side chain of styrene is predicted to produce trans or cis conformations of phenylvinylacetylene (t- and c-PVA), whereas C{sub 2}H addition to the ortho carbon in the ring is expected to lead to the formation of o-ethynylstyrene. Although various reaction channels may lead to a second ring closure and the formation of naphthalene, they are not competitive with the direct H loss channels producing PVAs and ethynylstyrenes. However, c-PVA and o-ethynylstyrene may undergo a second addition of the ethynyl radical to ultimately produce substituted naphthalene derivatives. {alpha}- and {beta}-additions of C{sub 2}H to the side chain in c-PVA are calculated to form 2-ethynyl-naphthalene with branching ratios of about 30% and 96%, respectively; the major product in the case of {alpha}-addition would be cis-1-hexene-3,5-diynyl-benzene produced by an immediate H elimination from the initial adduct. C{sub 2}H addition to the ethynyl side chain in o-ethynylstyrene is predicted to lead to the formation of 1-ethynyl-naphthalene as the dominant product. The C{sub 2}H + styrene {yields}t-PVA+ H/c-PVA+ H/o-ethynylstyrene, C{sub 2}H +c-PVA{yields} 2-ethynyl-naphthalene + H, and C{sub 2}H +o-ethynylstyrene {yields} 1-ethynyl-naphthalene + H reactions are calculated to occur without a barrier and with high exothermicity, with all intermediates, transition states, and products lying significantly lower in energy than the initial reactants, and hence to be fast even at very low temperature conditions prevailing in Titan's atmosphere or in the interstellar medium. If styrene and C{sub 2}H are available and overlap, the sequence of two C{sub 2}H additions can result in the closure of a second aromatic ring and thus provide a viable route to the formation of 1- or 2-ethynyl-naphthalene. The analogous mechanism can be extrapolated to the low-temperature growth of polycyclic aromatic hydrocarbons (PAH) in general, as a step from a vinyl-PAH to an ethynyl-substituted PAH with an extra aromatic ring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Observation and modeling of polycrystalline grain formation in Ge{sub 2}Sb{sub 2}Te{sub 5}

The relationship between the polycrystalline nature of phase change materials (such as Ge{sub 2}Sb{sub 2}Te{sub 5}) and the intermediate resistance states of phase change memory (PCM) devices has not been widely studied. A full understanding of such states will require knowledge of how polycrystalline grains form, how they interact with each other at various temperatures, and how the differing electrical (and thermal) characteristics within the grains and at their boundaries combine through percolation to produce the externally observed electrical (and thermal) characteristics of a PCM device. We address the first of these tasks (and introduce a vehicle for the second) by studying the formation of fcc polycrystalline grains from the as-deposited amorphous state in undoped Ge{sub 2}Sb{sub 2}Te{sub 5}. We perform ex situ transmission electron microscopy membrane experiments and then match these observations against numerical simulation. Ramped-anneal experiments show that the temperature ramp-rate strongly influences the median grain size. By truncating such ramped-anneal experiments at various peak temperatures, we convincingly demonstrate that the temperature range over which these grains are established is quite narrow. Subsequent annealing at elevated temperature appears to change these established distributions of grain sizes only slightly. Our numerical simulator--which models nuclei formation through classical nucleation theory and then tracks the subsequent time- and temperature-dependent growth of these grains--can match these experimental observations of initial grain distributions and crystallization temperature both qualitatively and quantitatively. These simulations show that the particular narrow temperature range over which crystallization occurs shifts as a function of temperature ramp-rate, which allows us to quantify the lower portions of the time-temperature-transformation map for Ge{sub 2}Sb{sub 2}Te{sub 5}. Future experiments and extensions of the simulator to investigate temperature-dependent interactions between neighboring grains, and to study nucleation from within the melt-quenched amorphous state, are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Structure and prospects of the simplest SO(10) GUTs

We recapitulate the latest results on the class of the simplest SO(10) grand unified models in which the GUTscale symmetry breaking is triggered by an adjoint Higgs representation. We argue that the minimal survival approximation traditionally used in the GUT-and seesaw-scale estimates tends to be blind to very interesting parts of the parameter space in which some of the intermediate-scale states necessary for non-supersymmetric unification of the SM gauge couplings can be as light as to leave their imprints in the TeV domain. The stringent minimal-survival-based estimates of the B - L scale are shown to be relaxed by as much as four orders of magnitude, thus admitting for a consistent implementation of the standard seesaw mechanism even without excessive fine-tuning implied by the previous studies. The prospects of the minimal renormalizable SO(10) GUT as a potential candidate for a well-calculable theory of proton decay are discussed in brief.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Low-temperature magnetic characterization of optimum and etch-damaged in-plane magnetic tunnel junctions

We describe low-temperature characterization of magnetic tunnel junctions (MTJs) patterned by reactive ion etching for spin-transfer-torque magnetic random access memory. Magnetotransport measurements of typical MTJs show increasing tunneling magnetoresistance (TMR) and larger coercive fields as temperature is decreased down to 10 K. However, MTJs selected from the high-resistance population of an MTJ array exhibit stable intermediate magnetic states when measured at low temperature and show TMR roll-off below 100 K. These non-ideal low-temperature behaviors arise from edge damage during the etch process and can have negative impacts on thermal stability of the MTJs.

36 MATERIALS SCIENCE↗
DOE OSTI2014

A general time-dependent route to Resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects

We present a new formulation of the time-dependent theory of Resonance-Raman spectroscopy (TD-RR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, Herzberg-Teller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TD-RR procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TD-RR implementation are validated against our previously proposed and well-tested time-independent procedure. Practical applications are illustrated with some closed- and open-shell medium-size molecules (anthracene, phenoxyl radical, benzyl radical) and the simulated spectra are compared to the experimental results. More complex and larger systems, not limited to organic compounds, can be also studied, as shown for the case of Tris(bipyridine)ruthenium(II) chloride.

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

Magnetothermopower, magnetic entropy change, and magnetoresistance in ferromagnetic cobaltites: R{sub 0.7}Sr{sub 0.3}CoO{sub 3} (R = La and Gd)

We compare the impact effect of external magnetic fields on the magnetic entropy (S{sub m}), electrical resistivity, and thermopower in two metallic oxides R{sub 0.7}Sr{sub 0.3}CoO{sub 3} that become ferromagnetic below T{sub C} = 240 K and 117 K for R = La{sup 3+}(4f{sup 0}) and Gd{sup 3+}(4f{sup 7}), respectively. While Gd{sub 0.7}Sr{sub 0.3}CoO{sub 3} shows unusually high values of negative magnetothermopower (≈−35.5%), magnetic entropy change (ΔS{sub m} ≈ −12 J/kg K), and negative magnetoresistance (≈−3.7%) at 10 K for a field change of 5 T, these effects are absent in the La sample at 10 K. We suggest that the large ΔS{sub m} arises from the field-induced suppression of spin fluctuations associated with localized 4f{sup 7} moments of Gd{sup 3+} ions, but magnetic interaction among Co ions dictates magnetoresistance and magnetothermopower. Magnetization data indicate that while Co{sup 3+} ions adopt intermediate spin state (S = 1) in the La compound, major fraction of them transforms into low spin state (S = 0) in the Gd sample. Hence, the Gd sample is microscopically heterogeneous with a mixture of ferromagnetic metallic and paramagnetic metallic clusters. Spin dependent scattering at the surface of ferromagnetic clusters may be the cause for the coexistence of magnetothermopower and magnetoresistance in this compound. A close correlation between the magnetoresistance and the magnetothermopower is reported.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Attosecond nanotechnology: NEMS of energy storage and nanostructural transformations in materials

The attosecond technology of the nanoelectromechanical system (NEMS) energy storage as active center fast transformation of nanostructures in materials is considered. The self-organizing relaxation of the NEMS active center containing nanocube of 256-atoms limited by planes (100) in the FCC lattice matrix of 4d-transition metals (Ru, Rh, Pd) is described by the quantum NEMS-kinetics (NK) method. Typical for these metals change of the NEMS active center physicochemical characteristics during the time of relaxation is presented. There are three types of intermediate quasistationary states of the NEMS active center. Their forms are plainly distinguishable. The full relaxed NEMS active centers (Ru{sub 256}, Rh{sub 256}, Pd{sub 256}) accumulate next storage energies: E{sub Ru} = 2.27 eV/at, E{sub Rh} = 1.67 eV/at, E{sub Pd} = 3.02 eV/at.

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

Composition-induced structural, electrical, and magnetic phase transitions in AX-type mixed-valence cobalt oxynitride epitaxial thin films

Synthesis of mid- to late-transition metal oxynitrides is generally difficult by conventional thermal ammonolysis because of thermal instability. In this letter, we synthesized epitaxial thin films of AX-type phase-pure cobalt oxynitrides (CoO{sub x}N{sub y}) by using nitrogen-plasma-assisted pulsed laser deposition and investigated their structural, electrical, and magnetic properties. The CoO{sub x}N{sub y} thin films with 0 ≤ y/(x + y) ≤ 0.63 grown on MgO (100) substrates showed a structural phase transition from rock salt (RS) to zinc blend at the nitrogen content y/(x + y) ∼ 0.5. As the nitrogen content increased, the room-temperature electrical resistivity of the CoO{sub x}N{sub y} thin films monotonically decreased from the order of 10{sup 5} Ω cm to 10{sup −4} Ω cm. Furthermore, we observed an insulator-to-metal transition at y/(x + y) ∼ 0.34 in the RS-CoO{sub x}N{sub y} phase, which has not yet been reported in Co{sup 2+}/Co{sup 3+} mixed-valence cobalt oxides with octahedral coordination. The low resistivity in the RS-CoO{sub x}N{sub y} phase, on the 10{sup −3} Ω cm order, may have originated from the intermediate spin state of Co{sup 3+} stabilized by the lowered crystal field symmetry of the CoO{sub 6−n}N{sub n} octahedra (n = 1, 2,…5). Magnetization measurements suggested that a magnetic phase transition occurred in the RS-CoO{sub x}N{sub y} films during the insulator-to-metal transition. These results demonstrate that low-temperature epitaxial growth is a promising approach for exploring novel electronic functionalities in oxynitrides.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗