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At least 1,243 records · Page 69

Solving the auroral-arc-generator question by using an electron beam to unambiguously connect critical magnetospheric measurements to auroral images

Here, an active mapping mission is described that unambiguously connects measurements in the Earth's magnetosphere to visible aurora in the atmosphere. The core of the mission is an electron-beam source operated on a spacecraft in the equatorial magnetosphere, with the electron beam traveling along the Earth's magnetic-field lines to the atmosphere, depositing its energy to create an optical beam-spot in the atmosphere at the footpoint of the spacecraft's magnetic-field line. This optical spot can be imaged by ground-based cameras, putting the location of the spacecraft's magnetic footpoint into the context of the optical aurora. Scientific instruments carried on the spacecraft make critical measurements of the properties of the magnetosphere at the locations where the magnetosphere powers the aurora, allowing the determination of the plasma-physics mechanisms by which the magnetosphere drives the aurora, in particular answering the outstanding question of how the magnetosphere drives low-latitude auroral arcs. Long-standing questions in magnetosphere-ionosphere coupling that have not been answered because we could not unambiguously connect locations in the magnetosphere with their image in the ionosphere will finally be addressed. In this paper the properties of a “standard” growth-phase auroral arc are collected, theories of the magnetospheric generation of auroral arcs are reviewed, and critical magnetospheric measurements to discern the mechanisms that drive auroral arcs are determined. Further, the plasma physics of the experiment is investigated, including spacecraft-charging mitigation, beam stability, beam scattering, and electron orbit theory. Tradeoffs (keV versus MeV) concerning the energy of the electron beam are enumerated.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Guided skyrmion motion along pinning array interfaces

We examine ac driven skyrmions interacting with the interface between two different obstacle array structures. We consider drive amplitudes at which skyrmions in a bulk obstacle lattice undergo only localized motion and show that when an obstacle lattice interface is introduced, directed skyrmion transport can occur along the interface. The skyrmions can be guided by a straight interface and can also turn corners to follow the interface. For a square obstacle lattice embedded in a square pinning array with a different obstacle radius, we find that skyrmions can undergo transport in all four primary symmetry directions under the same fixed ac drive. We map where localized or translating motion occurs as a function of the ac driving parameters. Our results suggest a new method for controlling skyrmion motion based on transport along obstacle lattice interfaces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A conceptual model for how to design for building envelope characteristics. Impact of thermal comfort intervals and thermal mass on commercial buildings in U.S. climates

The paper presents a simplified conceptual model for energy demand calculations based on building envelope characteristics, thermal mass and local climate. It is based on a network model and lumped analysis of the dynamic process. Characteristic parameters for the buildings are suggested; Driving temperature (DT), Driving temperature difference, (DTD), External Load Temperature (ELT), and Thermal Load Resistance (TLR). The Building Envelope Performance ( BEP 0 ), based on a controlled constant indoor temperature is introduced. Solution techniques using stable explicit forward differences based on analytical solutions are derived. The conceptual model has been used for mapping the Driving temperature difference and introduced two performance factors and . The first factor represents the effect of thermal comfort interval and thermal mass on the energy demand. The latter represents the ratio between cooling and heating energy demand. These three parameters and factors have been visualized on U.S. maps and enable a possibility to communicate the demand of energy, and cooling and the coupling to building characteristics, in a concise way.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Enriching OpenStreetMap network data for transportation applications: Insights into the impact of urban congestion on accessibility

OpenStreetMap (OSM) data is a valuable open-source resource for various transportation, traffic, and planning applications. However, OSM network data lack operating traffic speed information, which is critical for transport planning and operations. Addressing this shortcoming, this study leverages commercial vendor data (to serve as ground truth) with exogenous, open-source variables characterizing local transport infrastructure, land use, and demographic information to predict average congested traffic speeds on OSM networks. Three machine-learning models were tested and estimated for OSM links with and without speed limit information in the Denver metropolitan region. Among these, XGBoost performed best, with mean absolute errors of 3.27 and 3.62 mph for links with and without speed limits, respectively. The developed models accurately predicted traffic speeds for different hours and days of the week compared to ground truth data. Using these predicted speeds, drive accessibility scores were computed for the Denver region for different time periods using the Mobility Energy Productivity (MEP) metric to understand the impact of congestion on energy-efficient accessibility. Results show that congestion-adjusted drive accessibility can be significantly lower compared to accessibility calculated using free flow speeds. Specifically, weekday evening hours saw a 42 % drop in accessibility due to reduced speeds, particularly around downtown Denver. Across the Denver metro region, approximately half as many opportunities and jobs are accessible in under 20 min by car during the evening peak period relative to free flow conditions. These findings underscore the importance of using congestion-adjusted operating speeds rather than speed limits in accessibility calculations, as reliance on speed limits can substantially overestimate energy-efficient drive accessibility in large, car-centric cities susceptible to significant congestion. In conclusion, the methodology presented here could further enrich OSM network data, making them useful for an even broader range of transportation applications.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

An ultrafast laser pulse picker technique for high-average-current high-brightness photoinjectors

Beam diagnostics in high brightness photoinjectors requires that optical pulses from a high-power drive laser be picked up with an ultrahigh pulse contrast ratio and without temporal profile distortion. In high-average-current high-brightness photoinjectors, high-power drive lasers are routinely operated at GHz-level pulse repetition rate and it is challenging to achieve pulse picking without any pulse distortion. Here, we report on a new ultrafast pulse picker technique for beam diagnostics in high-average-current high-brightness photoinjectors. By efficiently combining an ultrafast low-power electro-optic modulator, high-power fiber laser amplifiers, a high-power Pockels Cell, and a frequency doubling module, we have successfully demonstrated optical bunch (30 pulses per bunch) pickup from a 704 MHz high-power drive laser and achieved a 10 6 :1 pulse contrast ratio and nearly zero pulse distortion. The performance of this pulse picking technique has been verified through beam characterization and electron cooling in the low energy RHIC electron cooling accelerator at Brookhaven National Laboratory.

43 PARTICLE ACCELERATORS↗

Dynamics of an inertially collapsing gas bubble between two parallel, rigid walls

The collapse of cavitation bubbles in channel flows can give rise to structural damage along neighbouring walls. Although the collapse of a bubble near a single wall has been studied extensively, less is known about bubble collapse between two walls, e.g. as in a channel. We conduct highly resolved, direct simulations of the Navier–Stokes equations to investigate the bubble dynamics and pressures produced by the collapse of a bubble between two parallel rigid walls. We examine the dependence of the dynamics and pressures on the initial bubble location, confinement and driving pressure. For a fixed initial stand-off distance, as the channel width increases the bubble volume, migration distance and re-entrant jet speed approach their single-wall counterparts. We obtain an expression for the minimum channel width at which the confinement does not affect the bubble dynamics depending on the driving pressure difference and initial stand-off distance. For a fixed channel width, varying stand-off distance reduced the maximum wall pressures in the channel relative to the single wall; the trend was consistent for three different driving pressures. Two different jetting behaviours are seen when the bubble is centred in the channel, depending on the channel width. Under significant confinement, wall-parallel re-entrant jets impinge upon each other and further intensify the collapse of the vortex ring.

Rodriguez, Jr, Mauro (ORCID:0000000305450265)↗

A hybrid full-wave Markov chain approach to calculating radio-frequency wave scattering from scrape-off layer filaments

The interaction of radio-frequency (RF) waves with edge turbulence modifies the incident wave spectrum, and can significantly affect RF heating and current drive in tokamaks. Previous lower hybrid (LH) scattering models have either used the weak-turbulence approximation, or treated more realistic, filamentary turbulence in the ray tracing limit. In this study, a new model is introduced which retains full-wave effects of RF scattering in filamentary turbulence. First, a Mie-scattering technique models the interaction of an incident wave with a single Gaussian filament. Next, an effective differential scattering width is derived for a statistical ensemble of filaments. Lastly, a Markov chain solves for the transmitted wave spectrum in slab geometry. This model is applied to LH launching for current drive. The resulting wave spectrum is asymmetrically broadened in angular wavenumber space. This asymmetry is not accounted for in previous LH scattering models. The modified wave spectrum is coupled to a ray tracing/Fokker–Planck solver (GENRAY/CQL3D) to study its impact on current drive. The resulting current profile is greatly altered, and there is significant increase in the on-axis current and decrease in the off-axis peaks. This is attributed to a portion of the modified wave spectrum that is strongly dampened on-axis during the first pass.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Collisional broadening of nonlinear resonant wave–particle interactions

A general procedure for understanding plasma behaviour when resonant wave–particle interactions are the sole destabilizing and transport mechanism or only heating and/or current drive source is highlighted without recourse to involved numerical or analytical treatments. These phenomena are characterized by transport that appears to be collisionless even though collisions play a central role in narrow collisional boundary layers. The order of magnitude estimates, which include nonlinear effects, are shown to provide expressions in agreement with the principal results of recent toroidal Alfvén eigenmode (TAE), toroidal magnetic field ripple, and heating and current drive treatments. More importantly, the retention of nonlinearities leads to new estimates of the alpha particle energy diffusivity at saturation for TAE modes, and the ripple threshold at which superbanana plateau evaluations of alpha particle transport are modified by nonlinear radial drift effects. In addition, the estimates indicate when quasilinear descriptions for heating and current drive will begin to fail. The phenomenological procedure demonstrates that in magnetic fusion relevant plasmas, narrow collisional boundary layers must be retained for resonant wave–particle interactions as they enhance the role of collisions, and make stochastic particle motion unlikely to be more important than other nonlinear processes.

Physics↗

Power-transfer and fixed-point analysis of sawtooth simulations of a current-carrying stellarator

Power-transfer and fixed-point analysis of previous NIMROD simulations (Roberds et al. , Phys. Plasmas , vol. 23, issue 9, 2016, 092513) improved the understanding of the effect of 3D (non-axisymmetric equilibrium) magnetic fields on sawtooth oscillations in the Compact Toroidal Hybrid (CTH) experiment. Computing the locations of order-1 fixed points, their Greene's residues, and local values for the rotational transform results in a description of CTH sawteeth consistent with Kadomtsev's model. A power-transfer analysis quantifies the distribution of energy among toroidal Fourier modes and their nonlinear interactions. The Lorentz power transfer drives sawtooth growth, and it is unambiguously interpreted as the flow of energy from toroidal mode $n'$ to mode $n$ , catalysed by $\boldsymbol {B}_{n-n'}$ . It has been reported previously that the CTH sawtooth frequency increases with the 3D field strength. This is attributed to an increased growth rate of the internal kink that drives sawtooth oscillations. Here, 3D fields remove energy from the kink, eliminating the possibility that these fields are an additional energy source that drives growth. Instead, 3D fields catalyse energy transfer from large-to-small scales, where magnetic reconnection is stronger. It is proposed that this energy transfer increases the reconnection rate at small scales, which is consistent with the increased growth rate observed at higher 3D field strengths.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Influence of External Conditions on the Black-to-Yellow Phase Transition of CsPbI 3 Based on First-Principles Calculations: Pressure and Moisture

All-inorganic CsPbI 3 perovskite has emerged as a promising candidate for next-generation solar cells. However, owing to the poor structural stability of black phase CsPbI 3 perovskite at room temperature, it spontaneously transforms to the yellow, photoinactive, nonperovskite phase at room temperature, limiting further development of CsPbI 3 perovskite solar cells. Here, to better understand the mechanism driving such undesirable phase transformation, we examine the thermodynamics and kinetics associated with γ-to-δ phase transformation using density functional theory calculation. A solid-state nudged elastic band method was employed to find minimum energy pathways assuming a concerted solid-state phase transformation between these two phases. The gas molecules representing atmospheric (H 2 O, O 2 , and N 2 ) and inert (Ar) ambient environments, as well as applied external pressure, were considered to examine the influence of external conditions on the black-to-yellow phase transition. Our calculation reveals that, with increasing pressure, the thermodynamic driving force for converting the γ-phase to the δ-phase increases, whereas a larger activation energy must be overcome for the phase transition to occur. We also investigate the moisture-induced phase transformation with an H 2 O molecule and its dissociated species (H + /OH – ) and demonstrate that the reaction energy barriers can be significantly lowered in the presence of H 2 O or OH – . On the other hand, other nonpolar species (O 2 , N 2 , and Ar) have a negligible effect on the phase transformation kinetics, while they might reduce the thermodynamic driving force for the phase transformation and suppress the undesirable phase transformation. Our theoretical prediction could support recent observations that the γ-to-δ phase transformation occurs rapidly and catalytically in the presence of moisture, whereas in dry argon and dry oxygen atmospheres, the γ-CsPbI 3 remains stable.

14 SOLAR ENERGY↗

Solvent Stabilization of Protic Oxonium/Ammonium Intermediates in Cation Radical Cyclization Reactions Investigated via Computational Approaches

Anodic intramolecular cyclization reactions have substantial synthetic utility for formation of cyclic carbon–carbon or carbon–heteroatom bonds. For cases of intramolecular trapping of a cation radical by a protic nucleophile, the cyclization step coincides with a substantial increase in substrate acidity and thus may exhibit particularly pronounced solvent effects. In this computational work, we employ both quantum chemical (QM) and quantum mechanics/molecular mechanics (QM/MM) methods to compute solvent effects on free energy profiles for cyclization and deprotonation reaction steps for cation radical intermediates of substrates representative for anodic intramolecular cyclizations. We find substantial solvent contribution to the thermodynamic driving force for cation radical cyclization; for example, methanol and tetrahydrofuran solvents provide ∼30–35 kJ/mol driving force to form cyclic oxonium cation radicals and ∼15–25 kJ/mol driving force to form cyclic ammonium cation radicals, compared to baseline reactions in dichloromethane solvent. Given that these solvent shifts are on par with the innate cyclization reaction thermodynamics, the choice of solvent plays a crucial role in promoting/driving the cation radical cyclization step. Methanol is particularly effective at facilitating rapid deprotonation of the cyclic cation radical intermediate, which may lead to the full electrochemical process (e.g., second electron transfer) proceeding heterogeneously at the anode.

Khan, Shahriar [ORNL] (ORCID:0000000289138430)↗

Ion Transport in Charged Membranes: Linking Electric-Field-Driven Mechanisms to Pore Size via Perturbation Analysis

Ion-exchange membranes are a critical component in electrochemical systems. Nevertheless, the understanding and modeling of ion transport within these porous structures have been limited by particular complexity reductions, either ignoring the dimensionality of their porous network architecture or imposing geometric assumptions (i.e., overlapping double layers). Before addressing this morphology-transport gap, a framework that relates the driving forces of transport to the geometry of a single pore is required. In this work, our modeling domain consists of a two-dimensional single pore with charged walls, connecting two identical electrolyte reservoirs. Using the Poisson-Nernst-Planck equations and regular perturbation theory, we decouple the electric fields and analyze the driving forces of ion transport, specifically electromigration and induced electroosmosis within the pore. These processes are described as analytical functions of the interaction aspect ratio, ?, defined as the ratio of the pore radius to the Debye length. Using this parameter, our study (i) describes the interplay between electromigrative and electroosmotic mechanisms that set ionic conductivity, (ii) identifies a dimensionless group of intrinsic electrolyte properties that indicates the predominant driving force, and (iii) provides a qualitative, confinement-dependent perspective on selectivity in ion-conducting membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control

Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C–N bond and forming a new C–C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. Furthermore, this work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Circularly Polarized Attosecond Pulses Enabled by an Azimuthal Phase and Polarization Grating

High-harmonic generation (HHG) is an extreme nonlinear optical process that can map the properties of an infrared driving laser beam onto short wavelength attosecond pulse trains. However, current techniques for generating circularly polarized high harmonics for probing magnetic materials and chiral systems have limitations: two-color collinear counter-rotating driving lasers result in a low cutoff photon energy, while single-color non-collinear counter-rotating schemes suffer from low conversion efficiency. In this work, we generate circularly polarized attosecond pulse trains by using a structured laser driver which has a rotating polarization and phase grating along the azimuthal coordinate. Furthermore, our experimental and numerical results demonstrate the production of left and right circularly polarized harmonics, which naturally separate upon propagation. Our approach uses a single laser color in a collinear geometry, that can be scaled for high efficiency. Simulations show this scheme can extend into the soft x-ray region when driven by mid-infrared driving lasers, while preserving the same high phase-matching cutoff photon energy as for linearly-polarized high harmonics.

attosecond science↗

Reorganization Energies for Interfacial Proton-Coupled Electron Transfer to a Water Oxidation Catalyst

The reorganization energy (λ) for interfacial electron transfer (ET) and proton-coupled electron transfer (PCET) from a conductive metal oxide (In 2 O 3 :Sn, ITO) to a surface-bound water oxidation catalyst were extracted from kinetic data measured as a function of the thermodynamic driving force. Visible light excitation resulted in rapid excited-state injection (k inj > 10 8 s -1 ) to the ITO, which photo-initiated the two interfacial reactions of interest. The rate constants for both reactions increased with the driving force, −ΔG°, to a saturating limit, k max , with rate constants consistently larger for ET than for PCET. Marcus-Gerischer analysis of the kinetic data provided the reorganization energy for interfacial PCET (0.90 ± 0.02 eV) and ET (0.40 ± 0.02 eV), respectively. The magnitude of k max for PCET was found to decrease with pH, behavior that was absent for ET. Both the decrease in k max and the larger reorganization energy for an unwanted competing PCET reaction from the ITO to the oxidized catalyst showcases a significant kinetic advantage for driving solar water oxidation at high pH. Computational analysis revealed a larger inner-sphere reorganization energy contribution for PCET than for ET arising from a more significant change in the Ru–O bond length for PCET. Extending Marcus-Gerischer theory to PCET by including the excited electron-proton vibronic states and the proton donor-acceptor motion provided an apparent reorganization energy of 1.01 eV. Furthermore, this study demonstrates that the Marcus-Gerischer theory initially developed for ET can be reliably extended to PCET for quantifying and interpreting reorganization energies observed experimentally.

Catalysts Kinetic parameters↗

Elucidation of Marcus Relationships for Hydride Transfer Reactions Involving Transition Metal Hydrides

The rate of hydride transfer from three Ir hydride complexes of the type Cp*Ir( R bpy)H + (Cp* = C 5 Me 5 ; R bpy = 4,4′-R-2,2′-bipyridine, R = OMe, H, CO 2 Me) to six N-methylacridinium ( R Acr + ) acceptors with electronically different substituents in the 2- or 2,7-positions were measured. Using the thermodynamic hydricity of the donors and the hydride affinity of the acceptors the thermodynamic driving forces for hydride transfer were determined. Brønsted plots, which correlate kinetic and thermodynamic hydricity, demonstrate distinct linear free energy relationships for each complex, with different Brønsted α values. Thus, at the same driving force hydride transfer from Cp*Ir( OMe bpy)H + is faster than for Cp*Ir(bpy)H + or Cp*Ir( CO2Me bpy)H + . Experimental and computational analyses are consistent with a concerted hydride transfer mechanism for all Ir complexes. As the thermodynamic driving force increases an earlier transition state is observed and all transition states also include π-stacking interactions between the donor and acceptor, which likely contribute to the different α values. The experimental data fits well to the Marcus model, enabling the determination of reorganization energies (λ) that range from 58 to 69 kcal mol -1 . These are lower than λ values for hydride transfer reactions involving organic donors and acceptors. This work provides a rare example of the correlation of kinetic and thermodynamic hydricity using only experimental data and shows that hydride transfer reactions involving metal hydrides can follow Marcus theory. Furthermore, the findings offer insight into controlling metal-catalyzed hydride transfer reactions, which is valuable for designing improved systems for a range of transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Operando Spectroscopic Analysis of Photovoltage Generation in Hematite Photoanodes

Solar-driven water splitting requires sufficient photovoltage to drive both water oxidation and proton reduction. Understanding the factors driving and limiting photovoltage generation is therefore crucial to optimizing photoelectrode design but has proven challenging to determine under operando conditions for photoanodes driving slow multiredox reactions such as water oxidation. In this work, operando optical spectroscopy is employed to measure the hole quasi-Fermi level (E F,p ) position in model hematite photoanodes as a function of applied bias and light intensity. The quasi-Fermi level splitting determined from these data are shown be in excellent agreement with the directly measured photovoltages, demonstrating the primarily electrochemical rather than primarily electrostatic origin of photovoltage in these photoelectrodes. E F,p pinning is observed at low light intensities and biases, indicative of hole trap states lying ∼0.2 eV above the valence band edge with a density of ∼1 nm −2 . Hole accumulation in these trap states is correlated with first order water oxidation. At higher light intensities and/or more anodic bias, E F,p becomes unpinned, assigned to saturation of these trap states, and correlated with the onset of third order water oxidation to molecular oxygen. Comparison with rate law analyses for other photoanodes indicates that such hole trap states may be a ubiquitous feature of metal oxides and suggests that materials processing strategies to suppress the density of such states would be a promising strategy to enhance photoanode performance.

Hematite↗

The Role of Coupled Feedbacks in the Decadal Variability of the Southern Hemisphere Eddy-Driven Jet

The Southern Hemisphere summertime eddy-driven jet and storm tracks have shifted poleward over the recent few decades. In previous studies, explanations have mainly stressed the influence of external forcing in driving this trend. Here we examine the role of internal tropical SST variability in controlling the austral summer jet’s poleward migration, with a focus on interdecadal time scales. The role of external forcing and internal variability are isolated by using a hierarchy of Community Earth System Model version 1 (CESM1) simulations, including the pre-industrial control, large ensemble, and pacemaker runs. Model simulations suggest that in the early twenty-first century, both external forcing and internal tropical Pacific SST variability are important in driving a positive southern annular mode (SAM) phase and a poleward migration of the eddy-driven jet. Additionally, Tropical Pacific SST variability, associated with the negative phase of the interdecadal Pacific oscillation (IPO), acts to shift the jet poleward over the southern Indian and southwestern Pacific Oceans and intensify the jet in the southeastern Pacific basin, while external forcing drives a significant poleward jet shift in the South Atlantic basin. In response to both external forcing and decadal Pacific SST variability, the transient eddy momentum flux convergence belt in the middle latitudes experiences a poleward migration due to the enhanced meridional temperature gradient, leading to a zonally symmetric southward migration of the eddy-driven jet. This mechanism distinguishes the influence of the IPO on the midlatitude circulation from the dynamical impact of ENSO, with the latter mainly promoting the subtropical wave-breaking critical latitude poleward and pushing the midlatitude jet to higher latitudes.

54 ENVIRONMENTAL SCIENCES↗