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The presentation summarizes work performed over summer 2015 related to Monte Carlo simulations. A flexible probability table interpolation scheme has been implemented and tested with results comparing favorably to the continuous phase-space on-the-fly approach.
A field-programmable gate array (FPGA) on a single lightweight, low-power integrated-circuit chip has been developed to implement an azimuth pre-filter (AzPF) for a synthetic-aperture radar (SAR) system. The AzPF is needed to enable more efficient use of data-transmission and data-processing resources: In broad terms, the AzPF reduces the volume of SAR data by effectively reducing the azimuth resolution, without loss of range resolution, during times when end users are willing to accept lower azimuth resolution as the price of rapid access to SAR imagery. The data-reduction factor is selectable at a decimation factor, M, of 2, 4, 8, 16, or 32 so that users can trade resolution against processing and transmission delays. In principle, azimuth filtering could be performed in the frequency domain by use of fast-Fourier-transform processors. However, in the AzPF, azimuth filtering is performed in the time domain by use of finite-impulse-response filters. The reason for choosing the time-domain approach over the frequency-domain approach is that the time-domain approach demands less memory and a lower memory-access rate. The AzPF operates on the raw digitized SAR data. The AzPF includes a digital in-phase/quadrature (I/Q) demodulator. In general, an I/Q demodulator effects a complex down-conversion of its input signal followed by low-pass filtering, which eliminates undesired sidebands. In the AzPF case, the I/Q demodulator takes offset video range echo data to the complex baseband domain, ensuring preservation of signal phase through the azimuth pre-filtering process. In general, in an SAR I/Q demodulator, the intermediate frequency (fI) is chosen to be a quarter of the range-sampling frequency and the pulse-repetition frequency (fPR) is chosen to be a multiple of fI. The AzPF also includes a polyphase spatial-domain pre-filter comprising four weighted integrate-and-dump filters with programmable decimation factors and overlapping phases. To prevent aliasing of signals, the bandwidth of the AzPF is made 80 percent of fPR/M. The choice of four as the number of overlapping phases is justified by prior research in which it was shown that a filter of length 4M can effect an acceptable transfer function. The figure depicts prototype hardware comprising the AzPF and ancillary electronic circuits. The hardware was found to satisfy performance requirements in real-time tests at a sampling rate of 100 MHz.
The projector quantum Monte-Carlo method is used to examine effects of long-range electron hopping on ferromagnetism in the Hubbard model on the generalized Shastry-Sutherland lattice. It is shown that the long-range electron hopping with the exponentially decaying hopping amplitudes t{sub ij}(α)∼e{sup −α|R{sub i}−R{sub j}|} stabilizes the ferromagnetic state for a wide range of electron hopping α, electron interactions U, and electron concentrations n above the half-filled band case n = 1. The critical value of the hopping parameter α{sub c}, below which the ferromagnetic state becomes stable, is calculated numerically and the ground-state phase diagram of the model in the n − α plane is presented for physically the most interesting case of the intermediate Coulomb interactions.
We report Fe(II)-catalyzed ferrihydrite (Fh) transformation to more crystalline iron (oxyhydr)oxide phases is a widely occurring geochemical process which has been extensively studied as a function of Fe(II)/Fh ratios at fixed Fh loadings. However, recent isolation of an intermediate Fe(III) species resulting from Fe(II)-Fh contact that facilitates transformation by dissolution/reprecipitation suggests that the kinetics and properties of product phases will instead depend mostly on its rate of accumulation to a critical concentration, consistent with principles in the classical nucleation theory (CNT). This suggests a dependence both on the loading of Fe(II) on the surface, which controls the rate of labile Fe(III) formation, as well as the available volume of solution, which also impacts how fast it can achieve its critical concentration to nucleate product phases. To specifically examine the latter effect, here we studied transformation of 15 mg Fh in 1 mM FeSO 4 solutions at pH 7.2 in batch suspensions of 30 mL, 150 mL, and 450 mL volumes. Time-dependent concentrations of aqueous Fe(II), surface-associated Fe(II), and resulting labile Fe(III) were monitored along with bulk solids characterization as a function of time. Transmission electron microscopy (TEM) was used to visualize the evolution of phases at identical locations on TEM grids. The collective results show that the rates of Fh loss and emergence of product lepidocrocite (Lp) and goethite (Gt) as well as their phase proportions, nucleation mode and morphological properties depend directly on the rate of accumulation of the labile Fe(III) precursor to its critical concentration, which in our experiments was controlled simply by varying the available volume of solution into which it enters. Statistical analyses of TEM image data suggest that while both heterogeneous and homogeneous nucleation occurred in all experiments, the former was increasingly favored at lower Fh/solution ratio due to its lower nucleation barrier being more favorable at attendant lower supersaturations of Fe(III).
Data from the 1350-1550 A bandpass channel of the 2.5-deg angular resolution extreme-ultraviolet telescope on the Apollo-Soyuz mission have been analyzed for stellar and airglow radiation contributions for the galactic latitude range above 30 deg. At intermediate latitudes, the resulting diffuse background is found to be correlated with the neutral hydrogen column density as determined by 21 cm radio data. This result, together with the observed anisotropy and mean intensity of the radiation field, is consistent with the hypothesis that scattering of galactic-plane starlight off dust grains having an albedo of 0.5 and a phase function coefficient of 0.5 is the primary source of the observed radiation field at the intermediate latitudes. The background intensity near the poles is, however, higher than expected from the H I column density and extinction measurements.
The Delplot method provides a means of analyzing conversion and selectivity data to derive a reaction sequence and has been applied so far to gas-phase or liquid-phase species. This study analyses the applicability of the method for catalytic reactions and considers for the first time adsorbed intermediates. The method is applied to a contact time study of the hydrodeoxygenation (HDO) of benzofuran at 0.5 MPa and 350 °C over a catalyst consisting of bimetallic CoPd phosphide supported on a potassium ion-exchanged ultra-stable Y (KUSY) zeolite. Both simple and detailed reaction networks were derived. The simple networks considered only gas-phase species and were modeled by a first-order sequence of steps, whereas the detailed network took into account adsorbed intermediates and was simulated using a rake mechanism. The networks were compared using F-statistics, which accounted for the differences in the number of fitting parameters. The detailed network gave a better fit to the experimental data because it represented a more realistic description of the transformation. A suggested sequence from the Delplot method was consistent with the simple network but not with the detailed network. The lack of applicability of the Delplot analysis to the network with adsorbates was linked to overly large equilibrium constants, a determination supported by Delplot fitting for a model sequence. Further, this study indicated the inapplicability of the Delplot method in determining reaction sequences that involve adsorbed species with large equilibrium constants for formation.
Polymorphs are solid materials with the same chemical composition but different crystallographic structures. A unique aspect of polymorphs is that they exhibit different physical properties, such as solubility, melting point, density, color, hardness, and bioavailability. Here, we synthesized polymorphs of colloidal crystals engineered with DNA by slow-cooling gold nanoparticle-core programmable atom equivalents (PAEs, particles with DNA sequences that control their bonding characteristics) under salt concentrations ranging from 0.5 to 4 M NaCl. This approach yielded a diverse set of single-crystalline phases with cubic, tetragonal, and hexagonal lattice symmetries. The structural transitions observed here arise solely from the modulation of interparticle repulsion via ionic strength and thermal processing. Notably, in certain cases, we observed diffusionless phase transformations, wherein the superlattices evolve from cubic to lower-symmetry tetragonal lattices. By tuning the thermal stability and salt concentration, we captured intermediate, metastable body-centered tetragonal structures during the slow-cool process, indicating that subtle changes in free energy can direct crystallization to low-symmetry phases. In conclusion, this study demonstrates that thermal and ionic parameters can be tuned to access and stabilize colloidal crystal polymorphs with emergent structures and interesting functional properties.
The extended charge carrier lifetime in metal halide perovskites is responsible for their excellent optoelectronic properties. Recent studies indicate that the superb device performance in these materials is intimately related to the organic cation dynamics. Here, we focus on the investigation of the two-dimensional hybrid perovskite, (C 8 H 17 NH 3 ) 2 PbI 4 (henceforth, OA + = C 8 H 17 NH 3 + ). Using elastic and quasielastic neutron scattering techniques and group theoretical analysis, we studied the structural phase transitions and rotational modes of the C 8 H 17 NH 3 + cation in (OA) 2 PbI 4 . Here, our results show that, in the high-temperature orthorhombic ( T > 310 K) phase, the OA + cation exhibits a combination of a twofold rotation of the NH 3 –CH 2 head group about the crystal c -axis with a characteristic relaxation time of ~6.2 ps, threefold rotations (C 3 ) of NH 3 and CH 3 terminal groups, and slow librations of the other atoms. Contrastingly, only the C 3 rotation is present in the intermediate-temperature orthorhombic (238 K < T < 310 K) and low-temperature monoclinic ( T < 238 K) phases.
Red quasars are thought to be an intermediate population between merger-driven star-forming galaxies in dust-enshrouded phase and normal quasars. If so, they are expected to have high accretion ratios, but their intrinsic dust extinction hampers reliable determination of Eddington ratios. Here, we compare the accretion rates of 16 red quasars at z ∼ 0.7 to those of normal type 1 quasars at the same redshift range. The red quasars are selected by their red colors in optical through near-infrared (NIR) and radio detection. The accretion rates of the red quasars are derived from the Pβ line in NIR spectra, which is obtained by the SpeX on the Infrared Telescope Facility in order to avoid the effects of dust extinction. We find that the measured Eddington ratios (L{sub bol}/L{sub Edd} ≃ 0.69) of red quasars are significantly higher than those of normal type 1 quasars, which is consistent with a scenario in which red quasars are the intermediate population and the black holes of red quasars grow very rapidly during such a stage.
Complex light metal hydrides are promising candidates for efficient, compact solid-state hydrogen storage. (De)hydrogenation of these materials often proceeds via multiple reaction intermediates, the energetics of which determine reversibility and kinetics. At the solid-state reaction front, molecular-level chemistry eventually drives the formation of bulk product phases. Therefore, a better understanding of realistic (de)hydrogenation behavior requires considering possible reaction products along all stages of morphological evolution, from molecular to bulk crystalline. Here, we use first-principles calculations to explore the interplay between intermediate morphology and reaction pathways. Employing representative complex metal hydride systems, we investigate the relative energetics of three distinct morphological stages that can be expressed by intermediates during solid-state reactions: i) dispersed molecules; ii) clustered molecular chains; and iii) condensed-phase crystals. Our results verify that the effective reaction energy landscape strongly depends on the morphological features and associated chemical environment, offering a possible explanation for observed discrepancies between X-ray diffraction and nuclear magnetic resonance measurements. Our theoretical understanding also provides physical and chemical insight into phase nucleation kinetics upon (de)hydrogenation of complex metal hydrides.
The δ → α phase transformation is a crucial step in the solution-growth process of formamidinium-based lead triiodide (FAPbI 3 ) hybrid organic–inorganic perovskite (HOIP) thin films for perovskite solar cells (PSCs). Because the addition of cesium (Cs) stabilizes the α phase of FAPbI 3 -based HOIPs, here our research focuses on FAPbI 3 (Cs) thin films. We show that having a large grain size in the δ-FAPbI 3 (Cs) non-perovskite intermediate films is essential for the growth of high-quality α-FAPbI 3 (Cs) HOIP thin films. Here grain coarsening and phase transformation occur simultaneously during the thermal annealing step. A large starting grain size in the δ-FAPbI 3 (Cs) thin films suppresses grain coarsening, precluding the formation of voids at the final α-FAPbI 3 (Cs)–substrate interfaces. PSCs based on the interface void-free α-FAPbI 3 (Cs) HOIP thin films are much more efficient and stable in the ambient atmosphere. This interesting finding inspired us to develop a simple room-temperature aging method for preparing coarse-grained δ-FAPbI 3 (Cs) intermediate films, which are subsequently converted to coarse-grained, high-quality α-FAPbI 3 (Cs) HOIP thin films. As a result, this study highlights the importance of microstructure meditation in the processing of formamidinium-based PSCs.
We report CrFeNi-based multi-principal element alloys (MPEAs) are being considered for nuclear applications because of their potentially superior mechanical properties and irradiation resistance. While the alloys appear stable against phase decomposition during ion irradiation performed at high dose rate, previous electron irradiation and thermal annealing studies suggested that some of them may be susceptible to phase decomposition. Therefore, to clarify the role of dose rate during ion irradiation on phase decomposition, a CrFeNiMn alloy was irradiated using Fe ions at 500 °C with an intermediate dose rate of 10 -4 dpa/s. Transmission electron microscopy and atom probe tomography observations revealed a high number density of NiMn precipitates, cavities, and dislocation loops, which had not previously been observed after ion irradiation at higher dose rates.
A new model of synthetic-aperture-radar (SAR) imaging of ocean waves is described. The model is based on mapping individual, slightly-rough surface facets through the SAR processor into the image and responses of the facets in the image domain are added together coherently to give the composite image. A windowing technique allows both the orbital motion and the phase velocity of the long waves to be included. It is determined that the azimuthal cut-off is due to a smearing of the response of the facets in the image induced by the random orbital motion of the intermediate large-scale waves and that the focus adjustment that gives the greatest image contrast is half the phase velocity of the dominant long wave. The optimal processing technique, however, may consist of spatially offsetting the multiple looks on the image domain to compensate the propagation of long waves during the integration time of the SAR.
By taking the nucleon-to-quark phase transition within a neutron star as an example, we present a thermodynamically consistent method to calculate the equation of state of ambient matter so that transitions that are intermediate to those of the familiar Maxwell and Gibbs constructions can be described. This method does not address the poorly known surface tension between the two phases microscopically (as, for example, in the calculation of the core pasta phases via the Wigner-Seitz approximation) but instead combines the local and global charge neutrality conditions characteristic of the Maxwell and Gibbs constructions, respectively. Overall charge neutrality is achieved by dividing the leptons to those that obey local charge neutrality (Maxwell) and those that maintain global charge neutrality (Gibbs). The equation of state is obtained by using equilibrium constraints derived from minimizing the total energy density. The results of this minimization are then used to calculate neutron star mass-radius curves, tidal deformabilities, equilibrium and adiabatic sound speeds, and nonradial g-mode oscillation frequencies for several intermediate constructions. Various quantities of interest transform smoothly from their Gibbs structures to those of Maxwell as the local-to-total electron ratio η, introduced to mimic the hadron-to-quark interface tension from 0 (Gibbs) to ∞ (Maxwell), is raised from 0 to 1. As a result, a notable exception is the g-mode frequency for the specific case of η = 1 for which a gap appears between the quark and hadronic branches.
We have systematically explored three approaches based on 9-fluorenylmethoxycarbonyl (Fmoc) chemistry solid phase peptide synthesis (SPPS) for the total chemical synthesis of the key depsipeptide intermediate for the efficient total chemical synthesis of insulin. The approaches used were: stepwise Fmoc chemistry SPPS; the “hybrid method”, in which maximally protected peptide segments made by Fmoc chemistry SPPS are condensed in solution; and, native chemical ligation using peptide-thioester segments generated by Fmoc chemistry SPPS. A key building block in all three approaches was a Glu[O-β-(Thr)] ester-linked dipeptide equipped with a set of orthogonal protecting groups compatible with Fmoc chemistry SPPS. We report the most effective method for the preparation of the 51 residue ester-linked polypeptide chain of ester insulin was the use of unprotected peptide-thioester segments, prepared from peptide-hydrazides synthesized by Fmoc chemistry SPPS, and condensed by native chemical ligation. High-resolution X-ray crystallography confirmed the disulfide pairings and three-dimensional structure of synthetic insulin lispro prepared from ester insulin lispro by this route. Further optimization of these pilot studies could yield an efficient total chemical synthesis of insulin lispro (Humalog) based on peptide synthesis by Fmoc chemistry SPPS.
NREL's thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient route to completely biogenic pyrolysis-based fuel precursors, fuels, and value-added chemicals depending on catalyst and process conditions. A near term pathway being developed uses these liquids for co-processing with petroleum feedstocks to assess biogenic carbon incorporation in hydrocarbon fuel feedstocks for potential refinery use. In this work, the impact of feedstock and catalyst on catalytic fast pyrolysis oil (CFPO) composition was determined with the oils then assessed for biogenic fuel production via FCC (fluidized catalytic cracking) co-processing. Biomass vapors were generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce clean vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled to a custom pyrolyzer system designed to produce consistent-composition pyrolysis vapors as feed to the DCR. Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available modified zeolite-based catalysts to produce CFPOs. These upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and simulated distillation (SIMDIS) to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. These exploratory vapor-phase-upgrading results demonstrated the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The FCC co-processing results demonstrated the feasibility of using CFPOs with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.
Li 1.1 V 3 O 8 is a promising cathode material for Li-ion batteries, because of its high theoretical capacity (362 mAh g-1) and good rate performance. In this study, the structural evolution of Li 1.1 V 3 O 8 material during electrochemical dis(charge) processes was investigated using a combination of theoretical calculations and experimental data. Density functional theory (DFT) was used to predict the intermediate structures at various lithiation states, as well as the stability of major phases. In order to validate these predictions, in situ X-ray diffraction (XRD) data was collected operando, allowing for the phase transformations to be monitored under current load and eliminating the possibilities of structural relaxation processes and environmental oxidation. Rietveld refinement was performed to fit the diffraction data with the DFT-derived structures and to analyze the fractions of major phases as a function of dis(charge). The DFT calculations identified three stable states that were validated by the in situ XRD result: a Li-poor α-phase (Li1), a Li-rich α-phase (Li2.5), and a β-phase (Li4). The DFT-predicted particle shape based on the surface energy of the (100), (001), and (010) planes rationalized the preferential orientation of Li 1.1 V 3 O 8 particles along the [010] direction in the electrode. Furthermore, the onset and offset of the α → β transition, as well as the phase fractions of α and β determined via in situ XRD, related well with the DFT-derived relative stability of each phase. Thus, by integrating DFT calculations with experimental work, this work provides a thorough understanding of the structural transformations in Li 1.1 V 3 O 8 during electrochemical dis(charge).
In this study, electrochemical ozone production (EOP), a six-electron water oxidation reaction, offers promising avenues for creating value-added oxidants and disinfectants. However, progress in this field is slowed by a dearth of understanding of fundamental reaction mechanisms. In this work, we combine experimental electrochemistry, spectroscopic detection of reactive oxygen species (ROS), oxygen-anion chemical ionization mass spectrometry, and computational quantum chemistry calculations to determine a plausible reaction mechanism on nickel- and antimony-doped tin oxide (Ni/Sb–SnO 2 , NATO), one of the most selective EOP catalysts. Antimony doping is shown to increase the conductivity of the catalyst, leading to improved electrochemical performance. Spectroscopic analysis and electrochemical experiments combined with quantum chemistry predictions reveal that hydrogen peroxide (H 2 O 2 ) is a critical reaction intermediate. We propose that leached Ni 4+ cations catalyze hydrogen peroxide into solution phase hydroperoxyl radicals ( • OOH); these radicals are subsequently oxidized to ozone. Isotopic product analysis shows that ozone is generated catalytically from water and corrosively from the catalyst oxide lattice without regeneration of lattice oxygens. Further quantum chemistry calculations and thermodynamic analysis suggest that the electrochemical corrosion of tin oxide itself might generate hydrogen peroxide, which is then catalyzed to ozone. The proposed pathways explain both the roles of dopants in NATO and its lack of stability. Our study interrogates the possibility that instability and electrochemical activity are intrinsically linked through the formation of ROS. In doing so, we provide the first mechanism for EOP that is consistent with computational and experimental results and highlight the central challenge of instability as a target for future research efforts.