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DOE OSTI2022

Overcoming Degradation Pathways to Achieve Stable Blue Perovskite Light-Emitting Diodes

Mixed halide (Br/Cl) perovskite nanocrystals (NCs) that represent an advanced blue emitter commonly suffer from spectral instability and poor lifespan; notably, the lack of understanding of the failure mechanisms of these devices has restricted the future progress. Here, we determine that the degradation of CsPbBr x Cl 3– x NCs containing blue light-emitting diodes (LEDs) is due to the combination of two effects. Cl – drift among adjoining NCs under an electric field is found to induce a Cl-deficient material region in multiple NC layers, which dominates the unstable electroluminescence and causes fast degradation in the corresponding devices. In comparison, the monolayer NC devices that feature restricted anion drift pathways exhibit better operational stability; however, excess hole injection is demonstrated to induce irreversible chlorine loss in NCs. Such a process that largely arises from electrochemical oxidation of Cl – initiates a mild device failure in operation of tens of minutes. Through revealing these mechanisms, we modulate the devices’ construction and operational conditions to achieve a longer lifespan.

14 SOLAR ENERGY↗

DOE OSTI2021

Suppression of ITG turbulence due to spectral shift during biasing induced H-mode on HBT-EP

Investigations of biasing induced H-mode discharges on HBT-EP show that the edge turbulence is consistent with the ion temperature gradient) mode and have allowed for the controlled observation of the effect of applied flow shear on the turbulence. Measurements of the radial wavenumber spectrum of floating potentials at the edge show that the turbulence intensity decreases with increasing shift in the spectrum average ⟨ k r ⟩ when increasing amounts of bias probe voltage (and increasing amounts of flow shear) is applied. This is in agreement with the spectral shift model [Staebler et al., Phys. Rev. Lett. 110, 055003 2013] for turbulence suppression via sheared flow. A shift in the wavenumber spectrum occurs at applied electrode voltages and currents below the threshold needed for an L–H transition, and a dithering transition is obtained when biasing near the threshold. Suppression of blob-filament turbulence in the scrape-off layer (SOL) precedes the L–H transition, with the SOL turbulence remaining low throughout the dithering phase, despite the modulation of turbulence levels in the nearby edge. This demonstrates that the SOL turbulence “decouples” from the edge turbulence. The spectral shift in the measured radial wavenumber is corroborated by the direct measurement of eddy tilt angle using a novel time delay analysis technique first developed for Doppler reflectometry [Pinzon et al., Plasma Phys. Controlled Fusion 61, 105009 (2019)] but adapted here for floating potential measurements.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2024

Integration and validation of some modules for modelling of high-speed chemically reactive flows in two-phase gas-droplet mixtures

Three modules are integrated into the built-in OpenFOAM rhoCentralFoam solver towards accurate and efficient modelling of high-speed chemically reactive flows in two-phase gas-droplet mixtures within the OpenFOAM 10.0 framework. The first module is the mixture-averaged diffusion model. The second module is the built-in OpenFOAM Lagrangian solver coupled with optimised droplet drag coefficient and convective heat transfer coefficient sub-models. The last module is a sparse stiff chemistry solver based on dynamic adaptive hybrid integration (AHI-S). The optimised droplet sub-models are first verified in correct implementation for subsequent simulations in this work. Further, they show good accuracy against experimental and analytical data in the modelling of ammonia droplet acceleration and cooling in the flowing and/or low-temperature air. The accuracy and efficiency gains related to the mixture-averaged diffusion model and the AHI-S chemistry solver are examined by simulating 1-D detonation propagation in ammonia droplet-free/laden ammoniaoxygen mixtures. Numerical results of detonation propagation speed, gaseous temperature, density, and species distributions around the induction zone show good agreement with experimental data and analytical solutions. Compared to the built-in OpenFOAM diffusion model, the mixture-averaged diffusion model provides different numerical predictions of pulsating instabilities in detonation propagation. It shows better accuracy in depicting the detonation structure within the droplet-free section attributed to improved multi-component diffusion modelling. Compared to the built-in OpenFOAM solver EulerImplicit (backward Euler), the AHI-S chemistry solver reduces the computational cost by around 50%. It achieves satisfactory accuracy in calculating detonation propagation speed within the droplet-free section with the optimal efficiency when the safety factor, β, equals 0.5.

42 ENGINEERING↗

DOE OSTI2024

Regulating the Electron Distribution of Metal-Oxygen for Enhanced Oxygen Stability in Li-rich Layered Cathodes

Li-rich Mn-based layered oxides (LLO) hold great promise as cathode materials for lithium-ion batteries (LIBs) due to their unique oxygen redox (OR) chemistry, which enables additional capacity. However, the LLOs face challenges related to the instability of their OR process due to the weak transition metal (TM)-oxygen bond, leading to oxygen loss and irreversible phase transition that results in severe capacity and voltage decay. Herein, a synergistic electronic regulation strategy of surface and interior structures to enhance oxygen stability is proposed. In the interior of the materials, the local electrons around TM and O atoms may be delocalized by surrounding Mo atoms, facilitating the formation of stronger TM—O bonds at high voltages. Besides, on the surface, the highly reactive O atoms with lone pairs of electrons are passivated by additional TM atoms, which provides a more stable TM—O framework. Hence, this strategy stabilizes the oxygen and hinders TM migration, which enhances the reversibility in structural evolution, leading to increased capacity and voltage retention. This work presents an efficient approach to enhance the performance of LLOs through surface-to-interior electronic structure modulation, while also contributing to a deeper understanding of their redox reaction.

25 ENERGY STORAGE↗

DOE OSTI2023

AToM: Advanced Tokamak Modeling Environment

Stability constraints play an important role in integrated modeling. The global plasma stability and macro-instabilities such as internal kink modes, neoclassical tearing modes, and edge localized perturbations limit the plasma performance and can result in large-scale transient events and plasma disruptions. These macro-instabilities can be also beneficial to the plasma performance. For example, the peeling models often lead to the edge localized modes (ELMs). However, the formation of stationary edge harmonic oscillations (EHOs) due to nonlinear interaction of peeling modes can result in a transition to the Quiescent H-mode (QH-mode) without ELMs. The profiles predicted with transport models need to be refined using the MHD stability constraints. This is important especially for transient and nonlinear stages of discharges such as ramp-up access to hybrid and steady state operation, and L- to H-mode transition as well as transition to the QH-mode. Several stability and MHD codes are already included in the OMFIT framework. These codes include BALOO, ELITE, GATO, M3DC1, MARS, and NIMROD. However, the verifications of stability constraints are currently mostly excluded from transport modeling workflows. The only exception is the EPED module which includes the ELITE predictions to limit the pedestal height. Here, we improved the OMFIT workflow to include stability calculations. Including the stability conditions to the integrated modeling workflow improved the robustness of the predictive modeling discharges. Being implemented in the workflow, the stability conditions can be also used for the stability analysis of experimental data. This improved the physics understanding of various discharge scenarios and can be used in experiment planning.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2019

Extratropical Large-Scale Traveling Weather Systems in the Southern Hemisphere on Mars

From late-autumn through early-spring, the middle- and high-latitudes of both hemispheres of Mars and its predominantly carbon-dioxide atmosphere support mean equator-to-pole thermal contrasts, and then, support a strong mean westerly polar vortex. Observations from orbiting spacecraft indicate that this intense mean baroclinicity-barotropicity supports large-scale eastward traveling weather systems (i.e., transient, traveling synoptic-period waves, on the order of the Rossby deformation scale). On Earth, extratropical weather disturbances arise from wind-shear instabilities, and these are critical components of the terrestrial global circulation. So it is the case for Mars. Large-scale traveling weather systems on Mars serve as agents in the transport of heat, momentum and scalar and tracer quantities (e.g., atmospheric dust, watervapor, ice clouds, chemical species, etc). Such weather systems interact with other large-scale atmospheric circulation components, namely, quasi-stationary (i.e., forced Rossby) modes; global thermal tidal modes; and then, upon large-/continental- geographical scales, upslope/ down-slope flows amongst high relief, low relief, impact basins, and volcanic rises, and more. The character of Mars' traveling extratropical weather disturbances in its southern hemisphere during late winter through early spring is investigated using a high-resolution Mars global climate model (i.e., Mars GCM), and one from the Agency's Mars Climate Modeling Center (MCMC) based at the NASA Ames Research Center. The climate model includes several complex atmospheric physical packages. With such physics modules, our global climate simulations present comparatively well with observations of the planet's current water cycle (Haberle et al.,2019). The climate model is "forced" with an annual dust cycle (i.e., nudged based on MGS/TES observations). Compared to the northern-hemisphere counterparts, the southern synoptic-period weather disturbances and accompanying frontal waves have smaller meridional and zonal scales, and are less intense. Influences of the zonally asymmetric (i.e., east-west varying) topography on southern large-scale weather are investigated, in addition to large-scale up-slope/down-slope flows and the diurnal cycle. A southern storm zone in late winter and early spring presents in the western hemisphere via orographic influences from the Tharsis highlands, and the Argyre and Hellas impact basins. Geographically localized transient-wave activity diagnostics are constructed that illuminate dynamical differences amongst the simulations and these are presented.

Hollingsworth, Jeffery L.↗

NASA NTRS2020

Mechanisms of Stationary Crossflow Instability Growth and Breakdown Induced by Forward-Facing Steps

An experimental study is performed to determine the mechanisms by which a forward-facing step impacts the growth and breakdown to turbulence of the stationary cross-flow instability. Particle image velocimetry measurements are obtained in the boundary layer of a 30◦swept flat plate with a pressure body. Step heights range from 53 % to 71 % of the boundary-layer thickness. The critical step height is approximately 60 % of the boundary-layer thickness for the current study, although it is also shown that the critical step height depends on the initial amplitude of the stationary cross-flow vortices. For the critical cases, the stationary cross-flow amplitude grows sharply downstream of the step, decays for a short region and then grows again. The initial growth region is linear, and can be explained primarily through the impact of the step on the mean flow. Namely, the step causes abrupt changes to the mean flow, resulting in large values of wall-normal shear, as well as highly inflectional profiles, due to either cross-flow reversal, separation or both. These inflectional profiles are highly unstable for the stationary cross-flow. Additionally,the reversed flow regions are significantly modulated by the stationary cross-flow vortices. The second region of growth occurs due to the stationary-cross-flow-induced modulation of the shear layer, which leads to multiple smaller wavelength stream wise vortices. High-frequency fluctuations indicate that the unsteady transition mechanism for the critical cases relates to the shedding of vortices downstream of reattachment of the modulated separated regions.

boundary layer stability↗

NASA NTRS1994

Testing the gravitational instability hypothesis?

We challenge a widely accepted assumption of observational cosmology: that successful reconstruction of observed galaxy density fields from measured galaxy velocity fields (or vice versa), using the methods of gravitational instability theory, implies that the observed large-scale structures and large-scale flows were produced by the action of gravity. This assumption is false, in that there exist nongravitational theories that pass the reconstruction tests and gravitational theories with certain forms of biased galaxy formation that fail them. Gravitational instability theory predicts specific correlations between large-scale velocity and mass density fields, but the same correlations arise in any model where (a) structures in the galaxy distribution grow from homogeneous initial conditions in a way that satisfies the continuity equation, and (b) the present-day velocity field is irrotational and proportional to the time-averaged velocity field. We demonstrate these assertions using analytical arguments and N-body simulations. If large-scale structure is formed by gravitational instability, then the ratio of the galaxy density contrast to the divergence of the velocity field yields an estimate of the density parameter Omega (or, more generally, an estimate of beta identically equal to Omega(exp 0.6)/b, where b is an assumed constant of proportionality between galaxy and mass density fluctuations. In nongravitational scenarios, the values of Omega or beta estimated in this way may fail to represent the true cosmological values. However, even if nongravitational forces initiate and shape the growth of structure, gravitationally induced accelerations can dominate the velocity field at late times, long after the action of any nongravitational impulses. The estimated beta approaches the true value in such cases, and in our numerical simulations the estimated beta values are reasonably accurate for both gravitational and nongravitational models. Reconstruction tests that show correlations between galaxy density and velocity fields can rule out some physically interesting models of large-scale structure. In particular, successful reconstructions constrain the nature of any bias between the galaxy and mass distributions, since processes that modulate the efficiency of galaxy formation on large scales in a way that violates the continuity equation also produce a mismatch between the observed galaxy density and the density inferred from the peculiar velocity field. We obtain successful reconstructions for a gravitational model with peaks biasing, but we also show examples of gravitational and nongravitational models that fail reconstruction tests because of more complicated modulations of galaxy formation.

Babul, Arif↗

DOE OSTI2025

Electrolytic gold plating, stripping, and ion transport dynamics through a solid-state iodide perovskite

The pronounced electrochemical reactivity between halide perovskites and metal electrodes can introduce mobile extrinsic metal ions which can cause device instability or enable novel functionalities. Here we systematically investigate the kinetics of gold cation (Au + ) migration in indium tin oxide (ITO)/methylammonium lead triiodide (MAPbI 3 )/Au model devices under long-term potentiostatic biasing. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) analyses reveal that Au + ions, electrochemically generated at the Au anode, traverse the perovskite layer with diffusion coefficients on the order of 10 −11 to 10 −10 cm 2 s −1 and are subsequently reduced at the cathode as Au 0 clusters, resembling metal plating behavior in electrolytic cells and solid-state batteries during charging. Furthermore, reversing the applied bias strips the plated Au 0 , revealing reversibility suitable for bipolar resistive switching devices and providing direct evidence of the electrochemical and ionic nature of Au transport within the perovskite matrix. Quantitatively determining diffusion coefficients and ion concentrations provides foundational inputs for future drift-diffusion modelling opportunities and allows us to relate our findings to implications on long term operation of devices like photovoltaic modules. These results clearly demonstrate the solid-state electrochemical nature of perovskite devices, highlight methods to be more quantitative about ion transport properties, provide and emphasize the importance of disentangling electro-, photo-, photoelectrochemical processes for understanding device performance and unlocking new functionalities.

14 SOLAR ENERGY↗

NASA NTRS1997

Identification of defective illegitimate recombinational repair of oxidatively-induced DNA double-strand breaks in ataxia-telangiectasia cells

Ataxia-telangiectasia (A-T) is an autosomal-recessive lethal human disease. Homozygotes suffer from a number of neurological disorders, as well as very high cancer incidence. Heterozygotes may also have a higher than normal risk of cancer, particularly for the breast. The gene responsible for the disease (ATM) has been cloned, but its role in mechanisms of the disease remain unknown. Cellular A-T phenotypes, such as radiosensitivity and genomic instability, suggest that a deficiency in the repair of DNA double-strand breaks (DSBs) may be the primary defect; however, overall levels of DSB rejoining appear normal. We used the shuttle vector, pZ189, containing an oxidatively-induced DSB, to compare the integrity of DSB rejoining in one normal and two A-T fibroblast cells lines. Mutation frequencies were two-fold higher in A-T cells, and the mutational spectrum was different. The majority of the mutations found in all three cell lines were deletions (44-63%). The DNA sequence analysis indicated that 17 of the 17 plasmids with deletion mutations in normal cells occurred between short direct-repeat sequences (removing one of the repeats plus the intervening sequences), implicating illegitimate recombination in DSB rejoining. The combined data from both A-T cell lines showed that 21 of 24 deletions did not involve direct-repeats sequences, implicating a defect in the illegitimate recombination pathway. These findings suggest that the A-T gene product may either directly participate in illegitimate recombination or modulate the pathway. Regardless, this defect is likely to be important to a mechanistic understanding of this lethal disease.

Non-NASA Center↗

NASA NTRS1995

Variability of accretion disks surrounding black holes: The role of inertial-acoustic mode instabilities

The global nonlinear time-dependent evolution of the inertial-acoustic mode instability in accretion disks surrounding black holes has been investigated. The viscous stress is assumed to be proportional to the gas pressure only, i.e., tau = alphap(sub g). It is found that an oscillatory nonsteady behavior exists in the inner regions of disks (r is less than 10r(sub g) where r(sub g) is the Schwarzschild radius) for sufficiently large alpha(greater than or approximately equal to 0.2) and for mass accretion rates less than about 0.3 times the Eddington value. The variations of the integrated bolometric luminosity from the disk, Delta L/L, are less than 3%. A power spectrum analysis of these variations reveals a power spectrum which can be fitted to a power-law function of the frequency Pis proportional to f(exp -gamma), with index gamma = 1.4-2.3 and a low-frequency feature at about 4 Hz in one case. In addition, a narrow peak centered at a frequency corresponding to the maximum epicyclic frequency of the disk at approximately 100-130 Hz and its first harmonic is also seen. The low-frequency modulations are remarkably similar to those observed in black hole candidate systems. The possible existence of a scattering corona in the inner region of the disk and/or other processes contributing to the power at high frequencies in the inner region of the accretion disk may make the detection of the high-frequency component difficult.

Chen, Xingming↗

DOE OSTI2026

Single-Particle Insights Into the Electronic Structure and Enhanced Stability of CsPbBr 3 /FAPbBr 3 Core/Crown Nanoplatelets at the Nanometer Scale

Colloidal perovskite nanoplatelets (NPLs), despite their exceptional optoelectronic properties, face significant challenges due to their intrinsic instability and trap-assisted non-radiative recombination. Although many studies employing surface engineering, such as selecting ligands or coating to passivate defects, have demonstrated improved optoelectronic properties, these enhancements are typically inferred from bulk-ensemble measurements; the effects at the single-particle level remain elusive. Here, we conduct single-particle-level studies using scanning tunneling spectroscopy (STS) on a unique core–crown system, CsPbBr 3 @FAPbBr 3 NPLs, where the lateral surfaces of the CsPbBr 3 core are coated with an FAPbBr 3 crown. Experimental density-of-states (DOS) analysis reveals a 47% reduction in deep-trap states in core-crown NPLs compared to core-only NPLs, consistent with nearly two-fold enhancements in photoluminescence quantum yields. Progressive I–V sweep measurements demonstrate superior electrical stability in core-crown NPLs, preserving band structure with minimal degradation, while core-only NPLs exhibit rapid bandgap shrinkage and trap formation. Density functional theory (DFT) calculations indicate that FA incorporation distorts Pb octahedral lattice, widening the bandgap. This study elucidates how surface engineering modulates charge localization, passivates defects, and enhances stability at the single-particle level. Moreover, by uncovering bias-induced trap states in single unpassivated NPLs, this study establishes a precise, robust approach for characterizing emerging perovskite nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS2001

A Cloud-Resolving Simulation of Hurricane Bob (1991): Storm Structure and Eyewall Buoyancy

A numerical simulation of Hurricane Bob (1991) is conducted using the Penn State University-National Center for Atmospheric Research mesoscale model MM5 with a horizontal grid spacing of 1.3 Km on the finest nested mesh The model produces a realistic hurricane that intensifies slowly during the period of fine-scale simulation. Time-averaged results reveal the effects of storm motion. vertical shear, beta gyres and deformation forcing on the structure of radial inflow, vertical motion, and precipitation. Instantaneous model fields show that radial inflow in the eyewall is very intense near the surface but transitions to strong low-level outflow near the top of the boundary layer. The low-level structure is modulated by a wavenumber 2 disturbance that rotates around the eyewall at half the speed of the maximum tangential winds and is consistent with a vortex Rossby edge wave. The statistical distribution of vertical velocity in the eyewall indicates that the eyewall is composed of a small number of intense updrafts that account for the majority of the upward mass flux rather than a more gradual and symmetric eyewall circulation, consistent with the concept of hot towers. Tongues of high equivalent potential temperature, Theta(sub e), are seen along the inner edge of the eyewall updraft and within the low-level outflow. This air originates from outside of the eyewall with the highest theta(sub e) air coming from the layer closest to the surface after penetrating closest to the center. Occasionally, high Theta(sub e), air within the eye is drawn into the eyewall updrafts. The high Theta(sub e), air rising within the eyewall is shown to be associated with positive eyewall buoyancy with sufficient convective available potential energy along its path to produce relatively strong convective updrafts. Although the requirements for conditional symmetric instability are met within the eyewall and the air parcel trajectories follow slanted paths, the radial displacement of air parcels in the low-level outflow moves the air parcel sufficiently far away from the upper- warm core that the air becomes unstable to vertical displacements. Hence, convective instability rather than symmetric instability accounts for the stronger updrafts in the eyewall.

Braun, Scott A.↗

DOE OSTI2020

Multiorbital charge-density wave excitations and concomitant phonon anomalies in Bi 2 Sr 2 LaCuO 6+δ

Charge-density waves (CDWs) are ubiquitous in underdoped cuprate superconductors. As a modulation of the valence electron density, CDWs in hole-doped cuprates possess both Cu-3d and O-2p orbital character owing to the strong hybridization of these orbitals near the Fermi level. Here, we investigate underdoped Bi 2 Sr 1.4 La 0.6 CuO 6+δ using resonant inelastic X-ray scattering (RIXS) and find that a short-range CDW exists at both Cu and O sublattices in the copper-oxide (CuO 2 ) planes with a comparable periodicity and correlation length. Furthermore, we uncover bond-stretching and bond-buckling phonon anomalies concomitant to the CDWs. Comparing to slightly overdoped Bi 2 Sr 1.8 La 0.2 CuO 6+δ , where neither CDWs nor phonon anomalies appear, we highlight that a sharp intensity anomaly is induced in the proximity of the CDW wavevector (Q CDW ) for the bond-buckling phonon, in concert with the diffused intensity enhancement of the bond-stretching phonon at wavevectors much greater than Q CDW . Our results provide a comprehensive picture of the quasistatic CDWs, their dispersive excitations, and associated electron-phonon anomalies, which are key for understanding the competing electronic instabilities in cuprates.

36 MATERIALS SCIENCE↗

NASA NTRS2011

AXIOM: Advanced X-Ray Imaging of the Magnetosphere

Planetary plasma and magnetic field environments can be studied in two complementary ways by in situ measurements, or by remote sensing. While the former provide precise information about plasma behaviour, instabilities and dynamics on local scales, the latter offers the global view necessary to understand the overall interaction of the magnetospheric plasma with the solar wind. Some parts of the Earth's magnetosphere have been remotely sensed, but the majority remains unexplored by this type of measurements. Here we propose a novel and more elegant approach employing remote X-ray imaging techniques, which are now possible thanks to the relatively recent discovery of solar wind charge exchange X-ray emissions in the vicinity of the Earth's magnetosphere. In this article we describe how an appropriately designed and located X-ray telescope, supported by simultaneous in situ measurements of the solar wind, can be used to image the dayside magnetosphere, magnetosheath and bow shock, with a temporal and spatial resolution sufficient to address several key outstanding questions concerning how the solar wind interacts with the Earth's magnetosphere on a global level. Global images of the dayside magnetospheric boundaries require vantage points well outside the magnetosphere. Our studies have led us to propose AXIOM: Advanced X-ray Imaging Of the Magnetosphere, a concept mission using a Vega launcher with a LISA Pathfinder-type Propulsion Module to place the spacecraft in a Lissajous orbit around the Earth Moon L1 point. The model payload consists of an X-ray Wide Field Imager, capable of both imaging and spectroscopy, and an in situ plasma and magnetic field measurement package. This package comprises a Proton-Alpha Sensor, designed to measure the bulk properties of the solar wind, an Ion Composition Analyser, to characterize the minor ion populations in the solar wind that cause charge exchange emission, and a Magnetometer, designed to measure the strength and direction of the solar wind magnetic field. We also show simulations that demonstrate how the proposed X-ray telescope design is capable of imaging the predicted emission from the dayside magnetosphere with the sensitivity and cadence required to achieve the science goals of the mission.

Branduardi-Raymont, G.↗

NASA NTRS2012

AXIOM: Advanced X-ray Imaging of the Magnetosphere

Planetary plasma and magnetic field environments can be studied in two complementary ways - by in situ measurements, or by remote sensing. While the former provide precise information about plasma behaviour, instabilities and dynamics on local scales, the latter offers the global view necessary to understand the overall interaction of the magnetospheric plasma with the solar wind. Some parts of the Earth's magnetosphere have been remotely sensed, but the majority remains unexplored by this type of measurements. Here we propose a novel and more elegant approach employing remote X-ray imaging techniques. which are now possible thanks to the relatively recent discovery of solar wind charge exchange X-ray emissions in the vicinity of the Earth's magnetosphere. In this article we describe how an appropriately designed and located. X-ray telescope, supported by simultaneous in situ measurements of the solar wind, can be used to image the dayside magnetosphere, magnetosheath and bow shock. with a temporal and spatial resolution sufficient to address several key outstanding questions concerning how the solar wind interacts with the Earth's magnetosphere on a global level. Global images of the dayside magnetospheric boundaries require vantage points well outside the magnetosphere. Our studies have led us to propose 'AXIOM: Advanced X-ray Imaging Of the Magnetosphere', a concept mission using a Vega launcher with a LISA Pathfinder-type Propulsion Module to place the spacecraft in a Lissajous orbit around the Earth - Moon Ll point. The model payload consists of an X-ray Wide Field Imager, capable of both imaging and spectroscopy, and an in situ plasma and magnetic field measurement package. This package comprises a Proton-Alpha Sensor, designed to measure the bulk properties of the solar wind, an Ion Composition Analyser, to characterize the minor ion populations in the solar wind that cause charge exchange emission, and a Magnetometer, designed to measure the strength and direction of the solar wind magnetic field. We also show simulations that demonstrate how the proposed X-ray telescope design is capable of imaging the predicted emission from the dayside magnetosphere with the sensitivity and cadence required to achieve the science goals of the mission.

Branduardi-Raymont, G.↗

DOE OSTI2024

Polymeric ionic liquids containing copper(I) and copper(II) ions as gas chromatographic stationary phases for olefin separations

Copper(I) ions (Cu + ) are used in olefin separations due to their olefin complexing ability and low cost, but their instability in the presence of water and gases limits their widespread use. Ionic liquids (ILs) have emerged as stabilizers of Cu + ions and prevent their degradation, providing high olefin separation efficiency. There is limited understanding into the role that polymeric ionic liquids (PILs), which possess similar structural characteristics to ILs, have on Cu + ion-olefin interactions. Moreover, copper ions with diverse oxidation states, including Cu + and Cu 2+ ions, have been rarely employed for olefin separations. In this study, gas chromatography (GC) is used to investigate the interaction strength of olefins to stationary phases composed of the 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 6 MIM + ][NTf 2 – ]) IL and the poly(1-hexyl-3-vinylimidazolium [NTf 2 – ]) (poly([C 6 VIM + ][NTf 2 – ])) PIL containing monovalent and divalent copper salts (i.e., [Cu + ][NTf 2 – ] and [Cu 2+ ]2[NTf 2 – ]). The chromatographic retention of alkenes, alkynes, dienes, and aromatic compounds was examined. Incorporation of the [Cu 2+ ]2[NTf 2 – ] salt into a stationary phase comprised of poly(dimethylsiloxane) resulted in strong retention of olefins, while its addition to the [C 6 MIM + ][NTf 2 – ] IL and poly([C 6 VIM + ][NTf 2 – ]) PIL allowed for the interaction strength to be modulated. Olefins exhibited greater affinities toward IL and PIL stationary phases containing the [Cu 2+ ]2[NTf 2 – ] salt compared to those with the [Cu + ][NTf 2 – ] salt. Elimination of water from both copper salts was observed to be an important factor in promoting olefin interactions, as evidenced by increased olefin retention upon exposure of the stationary phases to high temperatures. Furthermore, to evaluate the long-term thermal stability of the stationary phase, chromatographic retention of probes was measured on the [Cu 2+ ]2[NTf 2 – ]/[C 6 MIM + ][NTf 2 – ] IL stationary phase after its exposure to helium at a temperature of 110°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Particle-in-cell simulations of the critical ionization velocity effect in finite size clouds

The critical ionization velocity (CIV) mechanism in a finite size cloud is studied with a series of electrostatic particle-in-cell simulations. It is observed that an initial seed ionization, produced by non-CIV mechanisms, generates a cross-field ion beam which excites a modified beam-plasma instability (MBPI) with frequency in the range of the lower hybrid frequency. The excited waves accelerate electrons along the magnetic field up to the ion drift energy that exceeds the ionization energy of the neutral atoms. The heated electrons in turn enhance the ion beam by electron-neutral impact ionization, which establishes a positive feedback loop in maintaining the CIV process. It is also found that the efficiency of the CIV mechanism depends on the finite size of the gas cloud in the following ways: (1) Along the ambient magnetic field the finite size of the cloud, L (sub parallel), restricts the growth of the fastest growing mode, with a wavelength lambda (sub m parallel), of the MBPI. The parallel electron heating at wave saturation scales approximately as (L (sub parallel)/lambda (sub m parallel)) (exp 1/2); (2) Momentum coupling between the cloud and the ambient plasma via the Alfven waves occurs as a result of the finite size of the cloud in the direction perpendicular to both the ambient magnetic field and the neutral drift. This reduces exponentially with time the relative drift between the ambient plasma and the neutrals. The timescale is inversely proportional to the Alfven velocity. (3) The transvers e charge separation field across the cloud was found to result in the modulation of the beam velocity which reduces the parallel heating of electrons and increases the transverse acceleration of electrons. (4) Some energetic electrons are lost from the cloud along the magnetic field at a rate characterized by the acoustic velocity, instead of the electron thermal velocity. The loss of energetic electrons from the cloud seems to be larger in the direction of plasma drift relative to the neutrals, where the loss rate is characterized by the neutral drift velocity. It is also shown that a factor of 4 increase in the ambient plasma density, increases the CIV ionization yield by almost 2 orders of magnitude at the end of a typical run. It is concluded that a larger ambient plasma density can result in a larger CIV yield because of (1) larger seed ion production by non-CIV mechanisms, (2) smaller Alfven velocity and hence weak momentum coupling, and (3) smaller ratio of the ion beam density to the ambient ion density, and therefore a weaker modulation of the beam velocity. The simulation results are used to interpret various chemical release experiments in space.

Moghaddam-Taaheri, E.↗