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At least 685 records · Page 38

Benefits of a 4th Ice Class in the Simulated Radar Reflectivities of Convective Systems Using a Bulk Microphysics Scheme

Numerous cloud microphysical schemes designed for cloud and mesoscale models are currently in use, ranging from simple bulk to multi-moment, multi-class to explicit bin schemes. This study details the benefits of adding a 4th ice class (hail) to an already improved 3-class ice bulk microphysics scheme developed for the Goddard Cumulus Ensemble model based on Rutledge and Hobbs (1983,1984). Besides the addition and modification of several hail processes from Lin et al. (1983), further modifications were made to the 3-ice processes, including allowing greater ice super saturation and mitigating spurious evaporationsublimation in the saturation adjustment scheme, allowing graupelhail to become snow via vapor growth and hail to become graupel via riming, and the inclusion of a rain evaporation correction and vapor diffusivity factor. The improved 3-ice snowgraupel size-mapping schemes were adjusted to be more stable at higher mixing rations and to increase the aggregation effect for snow. A snow density mapping was also added. The new scheme was applied to an intense continental squall line and a weaker, loosely-organized continental case using three different hail intercepts. Peak simulated reflectivities agree well with radar for both the intense and weaker case and were better than earlier 3-ice versions when using a moderate and large intercept for hail, respectively. Simulated reflectivity distributions versus height were also improved versus radar in both cases compared to earlier 3-ice versions. The bin-based rain evaporation correction affected the squall line case more but did not change the overall agreement in reflectivity distributions.

bulk microphysics schemes↗

Grain subdivision and structural modifications by high-energy heavy ions in UO 2 with different initial grain size

Irradiation with 84 MeV Xe ions at peak fluence above 7 × 10 17 ions/cm 2 has been carried out on two UO 2 samples with different initial grain sizes at 300 °C and 500 °C. Characterization of both grain structure and bubble morphology has been performed using transmission electron microscopy, image analysis and precession electron diffraction. The bubble size in the large-grained sample was smaller than that in the standard-grain sample, confirming fission gas precipitation resistance in the former. The ion irradiation in the high electronic energy deposition range has caused formation of a large density of dislocations which resulted in grain polygonization for the sample with standard grain size, which was observed in multiple lamellas extracted next to each other at peak dose. The sample with large grains showed inconsistent behavior. In one case, dislocation pile-up occurred, but no sub-grain formation was observed. An adjacent location showed sub-grain formation, even if to less extent compared to the standard grain-size sample. Furthermore, these findings suggest a limited polygonization resistance in large-grained UO 2 compared to standard-grain UO 2 . Recrystallization of both sample surfaces was present, leaving unclear if this is a surface effect or a consequence of the highest energy deposition rate in this area.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Aldol Condensation and Esterification over Ti-Substituted *BEA Zeolite: Mechanisms and Effects of Pore Hydrophobicity

Aldol condensation and esterification reactions provide paths to upgrade ethanol and acetaldehyde to higher- value molecules useful as fuels or intermediates for the synthesis of polymers. Transition-metal-substituted BEA zeolites (M-BEA) catalyze these reactions; however, the mechanisms for these processes in M-BEA and the effects of incidental or purposefully included silanol groups are not reported. Here, we combine kinetic and spectroscopic measurements obtained during catalytic reactions of acetaldehyde (CH 3 CHO), ethanol (C 2 H 5 OH), and hydrogen (H 2 ) mixtures over a series of Ti-BEA catalysts that possess a known range of silanol group densities to examine the kinetic relevance of intervening steps and the impact of silanol groups on catalytic rates. Across all Ti-BEA, rates for aldol condensation and esterification increase with the pressure of CH 3 CHO; however, C 2 H 5 OH and H 2 O weakly inhibit the rates of these reactions. The substitution of CD 3 CDO for CH 3 CHO decreases aldol condensation rates slightly (~10%) but leads to greater esterification rates (2- to 5-fold). The kinetic isotope effects together with the measured dependence of rates on reactant pressures suggest that aldol condensation and esterification occur on unoccupied Ti sites and involve multiple kinetically relevant steps. CH 3 CHO deprotonates irreversibly, and the kinetically relevant nucleophilic attack of the enolate to CH 3 CHO* (i.e., adsorbed CH 3 CHO on Ti sites) leads to aldol products, while the nucleophilic attack of the enolate to C 2 H 5 OH* gives esters. Selectivities toward aldol condensation increase with the ratio of CH 3 CHO to C 2 H 5 OH pressure and with increases in the silanol density of the as-synthesized Ti-BEA. During catalysis, in situ infrared spectroscopy demonstrates that these silanol groups react with C 2 H 5 OH to form ethoxysilane groups (i.e., SiOC 2 H 5 ) that modify the polarity of the environment near Ti active sites. As initial silanol densities increase, steady-state turnover rates for aldol condensation and esterification increase by factors of 5 and 2, respectively. The changes in rates and selectivities among Ti-BEA catalysts likely reflect changes in excess free energies of transition states for enolization and nucleophilic attack of the enolate to adsorbed coreactants. The differences in excess stability report on the interactions among reactive intermediates at framework Ti atoms and the ethoxysilane and remaining silanol groups present. Furthermore, the in situ modification of these pore environments confers changes in the stability of reactive species in a manner that contradicts intuition when considering the initial state of the catalyst but can be reconciled after accounting for the formation of persistent alkoxy surface moieties in the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of solar radiation on the orbits of small particles

A modification of the Robertson (1937) equations of particle motion in the presence of solar radiation is developed which allows for partial reflection of sunlight as a result of rapid and varying particle rotations caused by interaction with the solar wind. The coefficients and forces in earlier forms of the equations are compared with those in the present equations, and secular rates of change of particle orbital elements are determined. Orbital dimensions are calculated in terms of time, probable sizes and densities of meteoric and cometary particles are estimated, and times of infall to the sun are computed for a particle moving in an almost circular orbit and a particle moving in an elliptical orbit of high eccentricity. Changes in orbital elements are also determined for particles from a long-period sun-grazing comet. The results show that the time of infall to the sun from a highly eccentric orbit is substantially shorter than from a circular orbit with a radius equal to the mean distance in the eccentric orbit. The possibility is considered that the free orbital kinetic energy of particles drawn into the sun may be the energy source for the solar corona.

Lyttleton, R. A.↗

Understanding the Impact of Return-Current Losses on the X-Ray Emission from Solar Flares

I obtain and examine the implications of one-dimensional analytic solutions for return-current losses on an initially power-law distribution of energetic electrons with a sharp low-energy cutoff in flare plasma with classical (collisional) resistivity. These solutions show, for example, that return-current losses are not sensitive to plasma density, but are sensitive to plasma temperature and the low energy cutoff of the injected nonthermal electron distribution. A characteristic distance from the electron injection site, x(sub rc), is derived. At distances less than x(sub rc) the electron flux density is not reduced by return-current losses, but plasma heating can be substantial in this region, in the upper, coronal part of the flare loop. Before the electrons reach the collisional thick-target region of the flare loop, an injected power-law electron distribution with a low-energy cutoff maintains that structure, but with a flat energy distribution below the cutoff energy, which is now determined by the total potential drop experienced by the electrons. Modifications due to the presence of collisional losses are discussed. I compare these results with earlier analytical results and with more recent numerical simulations. Emslie's 1980 conjecture that there is a maximum integrated X-ray source brightness on the order of 10(exp -15) photons per square centimeter per second per square centimeter is examined. I find that this is not actually a maximum brightness and its value is parameter dependent, but it is nevertheless a valuable benchmark for identifying return-current losses in hard X-ray spectra. I discuss an observational approach to identifying return-current losses in flare data, including identification of a return-current "bump" in X-ray light curves at low photon energies.

Holman, Gordon D.↗

Effect of Co-Reactants on Interfacial Oxidation in Atomic Layer Deposition of Oxides on Metal Surfaces

We have examined the ALD of Al 2 O 3 using TMA as the precursor and t-BuOH and H 2 O as the co-reactants, focusing on the effects of the latter on both the ALD process and the possible modification of the underlying substrate. We have employed a quartz-crystal microbalance (QCM) to monitor ALD in situ and in real-time, and the deposited thin films have been characterized using X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and X-ray reflectivity. Growth of thin films of Al 2 O 3 using TMA and either t-BuOH or H 2 O as the co-reactant at T = 285 °C produces thin films of similar physical properties (density, stoichiometry, minimal carbon incorporation), and the growth rate per cycle is similar for the two co-reactants at this temperature. At a lower temperature of T = 120 °C, the behavior is starkly different, where growth occurs with H 2 O but not with t-BuOH. At either process temperature, we find no evidence for significant coverages of a long-lived tert-butoxy species from the reaction of t-BuOH. Deposition of thin films of Al 2 O 3 on metal surfaces of Cu and Co has been examined for evidence of interfacial oxidation. While growth with either co-reactant does not lead to the oxidation of the underlying Cu substrate, use of H 2 O leads to the oxidation of Co, while use of t-BuOH as the co-reactant does not. Thermodynamic factors may affect early stages of growth as Al species will likely scavenge all free O species. In contrast, at later times diffusion of species through the deposited Al 2 O 3 thin film could result in oxidation at the Al 2 O 3 |metal interface, a process that is strongly hindered in the case of t-BuOH due to its size. Furthermore, this observation highlights the importance of the choice of the co-reactant concerning ALD of oxides on metal surfaces.

36 MATERIALS SCIENCE↗

Cause and impact of low-frequency chirping modes in DIII-D hybrid discharges

Significant variations in MHD activity and fast-ion transport are observed in the DIIID high-beta, steady-state hybrid discharges with a mixture of Electron Cyclotron (EC) waves and Neutral Beam Injection (NBI). When Electron Cyclotron Heating (ECH) or Current Drive (ECCD) is applied, Alfven Eigenmodes (AEs) are usually suppressed and replaced by low-frequency bursting modes. The analysis of a recently compiled database of hybrid discharges suggests that the change of the fast-ion pressure especially the perpendicular pressure is the main factor responsible for the instability transition. The lower ratio of fast-ion injection speed v inj to Alfven speed v alfven and slight drop of safety factor q min during ECCD may also facilitate the transition. The database shows that AEs mainly occur when the fast-ion fraction P f /P total is less than 0.53 and v inj /v alfven is greater than 0.50, while low-frequency bursting modes appear in the opposite regime. In this research, P f and P total are the central fast-ion pressure from classical prediction and total plasma pressure, respectively. The reason why the instability transition correlates with P f /P total and v inj /v alfven is that they can significantly modify the drive of low-frequency bursting modes and AEs. The explanation is supported by the observation that low-frequency bursting modes are rarely seen in the hybrids with NBI only, with EC waves and counter-NBI, or with high plasma density. A careful check of the low-frequency bursting modes suggests that they are mainly chirping (neoclassical) tearing modes [referred to as chirping (N)TM], i.e. the mode frequency firstly jumps up from the steady (N)TM frequency, then chirps down, and finally returns to the steady (N)TM frequency. Sometimes, the (N)TMs are fully stabilized and replaced with pure fishbones. Lastly, the resonance condition calculation and ’Kick’ model simulations suggest that (N)TMs and fishbones can interact through modification of the fast ion distribution in phase space, which influences the drive.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Methane Adsorption on Heteroatom-Modified Maquettes of Porous Carbon Surfaces

Experimental and theoretical studies disagree on the energetics of methane adsorption on carbon materials. However, this information is critical for the rational design and optimization of the structure and composition of adsorbents for natural gas storage. The delicate nature of dispersion interactions, polarization of both the adsorbent and the adsorbate, interplay between H-bonding and tetrel bonding, and induced dipole/Coulomb interactions inherent to methane physisorption require computational treatment at the highest possible level of theory. In this study, we employed the smallest reasonable computational model, a maquette of porous carbon surfaces with a central site for substitution and methane binding. The most accurate predictions of methane adsorption energetics were achieved by electron-correlated molecular orbital theory CCSD(T) and hybrid density functional theory MN15 calculations employing a saturated, all-electron basis set. Here, the characteristic geometry of methane adsorption on a carbon surface (“lander approach”) arises due to bonding interactions of the adsorbent π-system with the proximal H–C bonds of methane, in addition to tetrel bonding between the antibonding orbital of the distal C–H bond and the central atom of the maquette (C, B, or N). The polarization of the electron density, structural deformations, and the comprehensive energetic analysis clearly indicate a ∼3 kJ mol –1 preference for methane binding on the N-substituted maquette. The B-substituted maquette showed a comparable or lower binding energy than the unsubstituted, pure C model, depending on the level of theory employed. The calculated thermodynamic results indicate a strategy for incorporating electron-enriched substitutions (e.g., N) into carbon materials as a way to increase methane storage capacity over electron-deficient (e.g., B) modifications. The thermochemical analysis was revised for establishing a conceptual agreement between the experimental isosteric heat of adsorption and the binding enthalpies from statistical thermodynamics principles.

03 NATURAL GAS↗

Plasma kinetic processes in a strong d.c. magnetic field

Recent results in the kinetic theory of a strongly magnetized plasma are surveyed. Emphasis is on the electrostatic guiding-center plasma in two dimensions, in both the fluid and 'charged rod' descriptions. The basic kinetic description of the plasma is in terms of the statistically-distributed Fourier coefficients associated with the velocity and 'enstrophy' (charge density) fields. It is a universal tendency in such media for enstrophy to flow to shorter wavelengths but for energy to flow to longer wavelengths. A consequence of the energy flow to longer wavelengths is the generation of long-range order in the form of macroscopic vortices. These kinds of structure have been called 'convection cells' and can be extraordinarily efficient in transporting particles transverse to a magnetic field. The tendency to vortex formation can be disrupted by collisions between particles. Modifications of the Fokker-Planck equation for a plasma produced by a strong dc magnetic field are considered in both two and three dimensions.

Montgomery, D.↗

Global Survey of the Relationship Between Cloud Droplet Size and Albedo Using ISCCP

Aerosols affect climate through direct and indirect effects. The direct effect of aerosols (e.g., sulfates) includes reflection of sunlight back toward space and for some aerosols (e.g., smoke particles), absorption in the atmosphere; both effects cool the Earth's surface. The indirect effect of aerosols refers to the modification of cloud microphysical properties, thereby affecting the radiation balance. Higher concentrations of Cloud Condensation Nuclei (CCN) generally produce higher concentrations of cloud droplets, which are also usually assumed to lead to decreased cloud droplet sizes. The result is an increase in cloud albedo, producing a net radiative cooling, opposite to the warming caused by greenhouse gases (Charlson et al. 1992). The change in clouds that is directly induced by an increase of aerosol concentration is an increase of cloud droplet number density, N; but is is usually assumed that cloud droplet size decreases as if the water mass density Liquid Water Content (LWC) were constant. There is actually no reason why this should be the case. Shifting the cloud droplet size distribution to more numerous smaller droplets can change the relative rates of condensational and coalescence growth, leading to different LWC (e.g., Rossow 1978). Moreover, the resulting change in cloud albedo is usually ascribed to more efficient scattering by smaller droplets, when in fact it is the increase in droplet number density (assuming constant LWC) that produces the most important change in cloud albedo: e.g., holding N constant and decreasing the droplet size would actually decrease the scattering cross-section and, thus, the albedo much more than it is increased by the increased scattering efficiency.

Han, Qingyuan↗

PYSAT: Python Satellite Data Analysis Toolkit

A common problem in space science data analysis is combining complementary data sources that are provided and analyzed in different formats and programming languages. The Python Satellite Data Analysis Toolkit (pysat) addresses this issue by providing an open source toolkit that implements the general process of space science data analysis, from beginning to end, in an instrumentindependent manner. This toolkit uses an Instrument object that enables systematic analysis of science data from a variety of platforms within a single interface. Basic functions such as downloading, loading, and cleaning are included for all supported instruments. Common analysis routines are also included, which are instrument and data source independent. A nanokernel is used to provide instrument independence, it is attached to the Instrument object and mediates the systematic and arbitrary modification of loaded data. Pysat uses the nanokernel to improve the rigor of time series analysis, support onthefly orbit determination, and cleanly span file breaks. Pysat's functions and higherlevel scientific analysis features are validated through the use of unit testing. Further adoption by the community provides a set of scientific results produced by a common core, constituting a distributed heritage that supports the validity of the underlying processing and scientific output. These features are used to demonstrate consistency between derived electron density profiles and measured ion drifts, particularly downward ion drifts in the afternoon hours during extreme solar minimum. Pysat builds upon open source Python software that is freely available and encourages communitydriven development.

Stoneback, R.A.↗

Computational Workflow for Accelerated Molecular Design Using Quantum Chemical Simulations and Deep Learning Models

Efficient methods for searching the chemical space of molecular compounds are needed to automate and accelerate the design of new functional molecules such as pharmaceuticals. Given the high cost in both resources and time for experimental efforts, computational approaches play a key role in guiding the selection of promising molecules for further investigation. Here, we construct a workflow to accelerate design by combining approximate quantum chemical methods [i.e. density-functional tight-binding (DFTB)], a graph convolutional neural network (GCNN) surrogate model for chemical property prediction, and a masked language model (MLM) for molecule generation. Property data from the DFTB calculations are used to train the surrogate model; the surrogate model is used to score candidates generated by the MLM. The surrogate reduces computation time by orders of magnitude compared to the DFTB calculations, enabling an increased search of chemical space. Furthermore, the MLM generates a diverse set of chemical modifications based on pre-training from a large compound library. We utilize the workflow to search for near-infrared photoactive molecules by minimizing the predicted HOMO-LUMO gap as the target property. Our results show that the workflow can generate optimized molecules outside of the original training set, which suggests that iterations of the workflow could be useful for searching vast chemical spaces in a wide range of design problems.

Blanchard, Andrew↗

Nanoscale imaging of He-ion irradiation effects on amorphous TaO x toward electroforming-free neuromorphic functions

Resistive switching in thin films has been widely studied in a broad range of materials. Yet, the mechanisms behind electroresistive switching have been persistently difficult to decipher and control, in part due to their non-equilibrium nature. Here, we demonstrate new experimental approaches that can probe resistive switching phenomena, utilizing amorphous TaO x as a model material system. Specifically, we applied scanning microwave impedance microscopy and cathodoluminescence (CL) microscopy as direct probes of conductance and electronic structure, respectively. These methods provide direct evidence of the electronic state of TaO x despite its amorphous nature. For example, CL identifies characteristic impurity levels in TaO x , in agreement with first principles calculations. We applied these methods to investigate He-ion-beam irradiation as a path to activate conductivity of materials and enable electroforming-free control over resistive switching. However, we find that even though He-ions begin to modify the nature of bonds even at the lowest doses, the films' conductive properties exhibit remarkable stability with large displacement damage and they are driven to metallic states only at the limit of structural decomposition. Finally, we show that electroforming in a nanoscale junction can be carried out with a dissipated power of <20 nW, a much smaller value compared to earlier studies and one that minimizes irreversible structural modifications of the films. Importantly, the multimodal approach described here provides a new framework toward the theory/experiment guided design and optimization of electroresistive materials.

36 MATERIALS SCIENCE↗

Erosion and modification of SO2 ice by ion bombardment of the surface of Io

New measurements on the effect of slow ion bombardment of SO2 ice using Ar(+) in the 15-45 keV range are presented. Total yields for loss of SO2 are given along with the energy spectra of the ejected molecules and molecular fragments and information on the chemical changes induced by the ion bombardment. These data are used to estimate that the direct sputter ejection rate of sulfur into the Jovian plasma is of the order of 10 billion atoms/sq cm/s, that the erosion rate of fresh SO2 deposits due to sputtering is of the order of 0.001 cm/yr, and that a significant and possibly observable column density of SO3 can be produced in an SO2 front only for penetrating ion bombardment. Chemical activity occurs even in rather low-temperature SO2 ice bombardment by ions in the nuclear stopping region, and this activity is likely to increase with increasing temperature.

Johnson, R. E.↗

Breaking of Inversion Symmetry and Interlayer Electronic Coupling in Bilayer Graphene Heterostructure by Structural Implementation of High Electric Displacement Fields

Controlling the interlayer coupling in two-dimensional (2D) materials generates novel electronic and topological phases. Its effective implementation is commonly done with a transverse electric field. However, phases generated by high displacement fields are elusive in this standard approach. Here, we introduce an exceptionally large displacement field by structural modification of a model system: AB-stacked bilayer graphene (BLG) on a SiC(0001) surface. We show that upon intercalation of gadolinium, electronic states in the top graphene layers exhibit a significant difference in the on-site potential energy, which effectively breaks the interlayer coupling between them. As a result, for energies close to the corresponding Dirac points, the BLG system behaves like two electronically isolated single graphene layers. This is proven by local scanning tunneling microscopy (STM)/spectroscopy, corroborated by density functional theory, tight binding, and multiprobe STM transport. Further, the work presents metal intercalation as a promising approach for the synthesis of 2D graphene heterostructures with electronic phases generated by giant displacement fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emergent ferromagnetism and insulator-metal transition in δ-doped ultrathin ruthenates

Abstract Heterostructures of complex transition metal oxides are known to induce extraordinary emergent quantum states that arise from broken symmetry and other discontinuities at interfaces. Here we report the emergence of unusual, thickness-dependent properties in ultrathin CaRuO 3 films by insertion of a single isovalent SrO layer (referred to as δ-doping). While bulk CaRuO 3 is metallic and nonmagnetic, films thinner than or equal to ~15-unit cells (u.c.) are insulating though still nonmagnetic. However, δ-doping to middle of such CaRuO 3 films induces an insulator-to-metal transition and unusual ferromagnetism with strong magnetoresistive behavior. Atomically resolved imaging and density-functional-theory calculations reveal that the whole δ-doped film preserves the bulk-CaRuO 3 orthorhombic structure, while appreciable structural and electronic changes are highly localized near the SrO layer. The results highlight delicate nature of magnetic instability in CaRuO 3 and subtle effects that can alter it, especially the role of A-site cation in electronic and magnetic structure additional to lattice distortion in ruthenates. It also provides a practical approach to engineer material systems via highly localized modifications in their structure and composition that may offer new routes to the design of oxide electronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Application of mesh refinement to relativistic magnetic reconnection

During relativistic magnetic reconnection, antiparallel magnetic fields undergo a rapid change in topology, releasing a large amount of energy in the form of non-thermal particle acceleration. This work explores the application of mesh refinement to 2D reconnection simulations to efficiently model the inherent disparity in length-scales. We have systematically investigated the effects of mesh refinement and determined necessary modifications to the algorithm required to mitigate non-physical artifacts at the coarse–fine interface. We have used the ultrahigh-order pseudo-spectral analytical time-domain Maxwell solver to analyze how its use can mitigate the numerical dispersion that occurs with the finite-difference time-domain (or “Yee”) method. Absorbing layers are introduced at the coarse–fine interface to eliminate spurious effects that occur with mesh refinement. We also study how damping the electromagnetic fields and current density in the absorbing layer can help prevent the non-physical accumulation of charge and current density at the coarse–fine interface. Using a mesh refinement ratio of 8 for two-dimensional magnetic reconnection simulations, we obtained good agreement with the high-resolution baseline simulation, using only 36% of the macroparticles and 71% of the node-hours needed for the baseline. The methods presented here are especially applicable to 3D systems where higher memory savings are expected than in 2D, enabling comprehensive, computationally efficient 3D reconnection studies in the future.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Computed tomographic analysis of meteorite inclusions

The feasibility of obtaining nondestructively a cross-sectional display of very dense heterogeneous rocky specimens, whether lunar, terrestrial or meteoritic, by using a fourth generation computed tomographic (CT) scanner, with modifications to the software only, is discussed. A description of the scanner, and of the experimental and analytical procedures is given. Using this technique, the interior of heterogeneous materials such as Allende can be probed nondestructively. The regions of material with high and low atomic numbers are displayed quickly; the object can then be cut to obtain for analysis just the areas of interest. A comparison of this technique with conventional industrial and medical techniques is made in terms of image resolution and density distribution display precision.

Arnold, J. R.↗