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At least 1,423 records · Page 79

In-situ synthesis of porous metal fluoride@carbon composite via simultaneous etching/fluorination enabled superior Li storage performance

Transition metal fluorides as Li-free conversion-type cathode materials have high theoretical specific capacities, however, their preparation strategy, sluggish electrochemical kinetic and poor cyclability have impeded their wide adoption in lithium-ion batteries. Herein, a facile in-situ synthesis of porous metal-fluoride-carbon composites is accomplished via simultaneous polytetrafluorethylene-based hard template etching and metal fluorination. This not only facilitates fast electron transfer and lithium-ion diffusion kinetics, but also buffers severe volume fluctuation during lithiation/delithation and enables the formation of a uniform and thin Li 2 CO 3 /LiF-rich cathode-electrolyte interphase. Here, as a proof of concept, the as-prepared porous FeF 3 @C (p-FeF 3 @C) indeed exhibits a high specific capacity of 230 mAh g -1 at 0.1 C together with an excellent capacity retention of 92.5% at 1 C for 200-cycles. Moreover, the practicality of the strategy is demonstrated by the superb electrochemical performance of the full-cells coupled with pre-lithiated graphite anodes. Therefore, the proposed novel synthetic strategy will enlighten the future design of high-performance metal-fluoride-carbon composites with porous structure for energy storage applications.

25 ENERGY STORAGE↗

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd

The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. Here, we examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al 2 O 3 . Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt–CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt–CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal–C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd–CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.

desorption↗

Coupled cluster benchmarks of large noncovalent complexes: The L7 dataset as well as DNA–ellipticine and buckycatcher–fullerene

In this work, benchmark binding energies for dispersion-bound complexes in the L7 dataset, the DNA–ellipticine intercalation complex, and the buckycatcher–C60 complex with 120 heavy atoms using a focal-point method based on the canonical form of second-order Møller−Plesset theory (MP2) and the domain based local pair natural orbital scheme for the coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set (CBS) limit are reported. This work allows for increased confidence given the agreement with respect to values recently obtained using the local natural orbital CCSD(T) for L7 and the canonical CCSD(T)/CBS result for the coronene dimer (C2C2PD). Therefore, these results can be considered pushing the CCSD(T)/CBS binding benchmark to the hundred-atom scale. The disagreements between the two state-of-the-art methods, CCSD(T) and fixed-node diffusion Monte Carlo, are substantial with at least 2.0 (∼10%), 1.9 (∼5%), and 10.3 kcal/mol (∼25%) differences for C2C2PD in L7, DNA–ellipticine, and buckycatcher–C60, respectively. Such sizable discrepancy above “chemical accuracy” for large noncovalent complexes indicates how challenging it is to obtain benchmark binding interactions for systems beyond small molecules, although the three up-to-date density functionals, PBE0+D4, ωB97M-V, and B97M-V, agree better with CCSD(T) for these large systems. In addition to reporting these values, different basis sets and various CBS extrapolation parameters for Hartree–Fock and MP2 correlation energies were tested for the first time in large noncovalent complexes with the goal of providing some indications toward optimal cost effective routes to approach the CBS limit without substantial loss in quality.

Ballesteros, Francisco (ORCID:0000000325732307)↗

Numerical thermalization in 2D PIC simulations: Practical estimates for low-temperature plasma simulations

The process of numerical thermalization in particle-in-cell (PIC) simulations has been studied extensively. It is analogous to Coulomb collisions in real plasmas, causing particle velocity distributions (VDFs) to evolve toward a Maxwellian as macroparticles experience polarization drag and resonantly interact with the fluctuation spectrum. This paper presents a practical tutorial on the effects of numerical thermalization in 2D PIC applications. Scenarios of interest include simulations, which must be run for many thousands of plasma periods and contain a population of cold electrons that leave the simulation space very slowly. This is particularly relevant to many low-temperature plasma discharges and materials processing applications. We present numerical drag and diffusion coefficients and their associated timescales for a variety of grid resolutions, discussing the circumstances under which the electron VDF is modified by numerical thermalization. Though the effects described here have been known for many decades, direct comparison of analytically derived, velocity-dependent numerical relaxation timescales to those of other relevant processes has not often been applied in practice due to complications that arise in calculating thermalization rates in 1D simulations. Using these comparisons, we estimate the impact of numerical thermalization in several examples of low-temperature plasma applications including capacitively coupled plasma discharges, inductively coupled plasma discharges, beam plasmas, and hollow cathode discharges. Finally, we discuss possible strategies for mitigating numerical relaxation effects in 2D PIC simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Negligible magnetic losses at low temperatures in liquid phase epitaxy grown Y 3 Fe 5 O 12 films

Yttrium iron garnet (Y 3 Fe 5 O 12 ; YIG) has a unique combination of low magnetic damping, high spin-wave conductivity, and insulating properties that make it a highly attractive material for a variety of applications in the fields of magnetics and spintronics. While the room-temperature magnetization dynamics of YIG have been extensively studied, there are limited reports correlating the low-temperature magnetization dynamics to the material structure or growth method. Here, in this study, we investigate liquid phase epitaxy grown YIG films and their magnetization dynamics at temperatures down to 10 K. We show there is a negligible increase in the ferromagnetic resonance linewidth down to 10 K, which is unique when compared with YIG films grown by other deposition methods. From the broadband ferromagnetic resonance measurements, polarized neutron reflectivity, and scanning transmission electron microscopy, we conclude that these liquid phase epitaxy grown films have negligible rare-earth impurities present, specifically the suppression of Gd diffusion from the Gd 3 Ga 5 O 12 (GGG) substrate into the Y 3 Fe 5 O 12 film, and therefore negligible magnetic losses attributed to the slow-relaxation mechanism. Overall, liquid phase epitaxy YIG films have a YIG/GGG interface that is five times sharper and have ten times lower ferromagnetic resonance linewidths below 50 K than comparable YIG films by other deposition methods. Thus, liquid phase epitaxy grown YIG films are ideal for low-temperature experiments/applications that require low magnetic losses, such as quantum transduction and manipulation via magnon coupling.

36 MATERIALS SCIENCE↗

The treatment of convected vortices in compressible potential flow

A method is described for incorporating line vortices into the three dimensional compressible potential flow equation. A modified Biot-Savart law is used to compute a vortical velocity field, which is added to the gradient of the potential to form a total velocity. A rapidly converging approximate factorization (AFZ) scheme is then used to compute a potential such that the modified potential flow equation as well as the appropriate boundary conditions, based on total velocity, are satisfied. As part of a coupled iteration procedure, the positions of the line vortices are computed so that they convect with the total flow. The method is used to compute the field due to a single line vortex convecting past a wing. This represents an approximation of the effect of a canard or other lifting surface ahead of the wing, which sheds a tip vortex. It is seen that the flow field is substantially modified by the passage of the vortex. Unlike Euler equation schemes, which are also used to compute these flows, the solutions exhibit no numerical diffusion: The convected vortices retain their initial upstream width. Euler solutions, on the other hand, involve a vorticity which is numerically convected in an Eulerian frame and, unless extensive adaptive grid refinement is used they result in vortices with spread as they convect. Also, the potential flow method requires approximately two orders of magnitude less computing time and much less computer storage than the Euler methods.

Steinhoff, J.↗

Slewing and vibration control of the SCOLE

A discussion of Slewing and Vibration Control makes the following conclusions: (1) A 2-stage approach is feasible and promising for rapid slewing and precision pointing of SCOLE; (2) Not all bang-bang type of time-minimized slew maneuvers will excite large structural vibrations in SCOLE; and (3) Modal dashpots can be a concentrated high-power vibration control, as well as the usual diffuse (broadband, low-power (low-authority) control. The following recommendations are made: (1) Limit the magnitude of applied forces on reflector to either the 25-lb limit of vernier thrusters on the real Space Shuttle or the 150-lb level equivalent to the cold-gas jets of laboratory SCOLE; (2) to complete stage 2, add an integrated design of LQF/LTR (Linear-Quadratic-Gaussian/Loop-Transfer Recovery) and Modal Dashpots; and, (3) Validate the 2-stage approach using the SCOLE laboratory facility with a comprehensive sequence of integrated designs and experiments coupling nonlinear rigid-body motions with flexible-body dynamics.

Lin, Jiguan Gene↗

Additive Runge-Kutta Schemes for Convection-Diffusion-Reaction Equations

Additive Runge-Kutta (ARK) methods are investigated for application to the spatially discretized one- dimensional convection-diffusion-reaction (CDR) equations. Accuracy, stability, conservation, and dense-output are first considered for the general case when N different Runge-Kutta methods are grouped into a single composite method. Then, implicit-explicit, (N = 2), additive Runge-Kutta (ARK(sub 2)) methods from third- to fifth-order are presented that allow for integration of stiff terms by an L-stable, stiffly-accurate explicit, singly diagonally implicit Runge-Kutta (ESDIRK) method while the nonstiff terms are integrated with a traditional explicit Runge-Kutta method (ERK). Coupling error terms of the partitioned method are of equal order to those of the elemental methods. Derived ARK(sub 2) methods have vanishing stability functions for very large values of the stiff scaled eigenvalue, z['] yields -infinity, and retain high stability efficiency in the absence of stiffness, z['] yield 0. Extrapolation-type stage- value predictors are provided based on dense-output formulae. Optimized methods minimize both leading order ARK(sub 2) error terms and Butcher coefficient magnitudes as well as maximize conservation properties. Numerical tests of the new schemes on a CDR problem show negligible stiffness leakage and near classical order convergence rates. However, tests on three simple singular-perturbation problems reveal generally predictable order reduction. Error control is best managed with a PID-controller. While results for the fifth-order method are disappointing, both the new third- and fourth-order methods are at least as efficient as existing ARK(sub 2) methods.

Kennedy, Christopher A.↗

Analysis of Thermal and Reaction Times for Hydrogen Reduction of Lunar Regolith

System analysis of oxygen production by hydrogen reduction of lunar regolith has shown the importance of the relative time scales for regolith heating and chemical reaction to overall performance. These values determine the sizing and power requirements of the system and also impact the number and operational phasing of reaction chambers. In this paper, a Nusselt number correlation analysis is performed to determine the heat transfer rates and regolith heat up times in a fluidized bed reactor heated by a central heating element (e.g., a resistively heated rod, or a solar concentrator heat pipe). A coupled chemical and transport model has also been developed for the chemical reduction of regolith by a continuous flow of hydrogen. The regolith conversion occurs on the surfaces of and within the regolith particles. Several important quantities are identified as a result of the above analyses. Reactor scale parameters include the void fraction (i.e., the fraction of the reactor volume not occupied by the regolith particles) and the residence time of hydrogen in the reactor. Particle scale quantities include the particle Reynolds number, the Archimedes number, and the time needed for hydrogen to diffuse into the pores of the regolith particles. The analysis is used to determine the heat up and reaction times and its application to NASA s oxygen production system modeling tool is noted.

Hegde, U.↗

Analysis of Thermal and Reaction Times for Hydrogen Reduction of Lunar Regolith

System analysis of oxygen production by hydrogen reduction of lunar regolith has shown the importance of the relative time scales for regolith heating and chemical reaction to overall performance. These values determine the sizing and power requirements of the system and also impact the number and operational phasing of reaction chambers. In this paper, a Nusselt number correlation analysis is performed to determine the heat transfer rates and regolith heat up times in a fluidized bed reactor heated by a central heating element (e.g., a resistively heated rod, or a solar concentrator heat pipe). A coupled chemical and transport model has also been developed for the chemical reduction of regolith by a continuous flow of hydrogen. The regolith conversion occurs on the surfaces of and within the regolith particles. Several important quantities are identified as a result of the above analyses. Reactor scale parameters include the void fraction (i.e., the fraction of the reactor volume not occupied by the regolith particles) and the residence time of hydrogen in the reactor. Particle scale quantities include the particle Reynolds number, the Archimedes number, and the time needed for hydrogen to diffuse into the pores of the regolith particles. The analysis is used to determine the heat up and reaction times and its application to NASA s oxygen production system modeling tool is noted.

Hegde, U.↗

Xenon Fractionation, Hydrogen Escape, and the Oxidation of the Earth

Xenon in Earth's atmosphere is severely mass fractionated and depleted compared to any plausible solar system source material, yet Kr is unfractionated. These observations seem to imply that Xe has escaped from Earth. But to date no process has been identified that can cause Xe, which is heavier than Kr, to escape while Kr does not. Vigorous hydrodynamic hydrogen escape can produce mass fractionation in heavy gases. The required hydrogen flux is very high but within the possible range permitted by solar Extreme Ultraviolet radiation (EUV, which here means radiation at wavelengths short enough to be absorbed efficiently by hydrogen) heating when Earth was on the order of 100 Myrs old or younger. However this model cannot explain why Xe escapes but Kr does not. Recently, what appears to be ancient atmospheric xenon has been recovered from several very ancient (3-3.5 Ga) terrestrial hydrothermal barites and cherts. What is eye-catching about this ancient Xe is that it is less fractionated that Xe in modern air. In other words, it appears that a process was active on Earth some 3 to 3.5 billion years ago that caused xenon to fractionate. By this time the Sun was no longer the EUV source that it used to. If xenon was being fractionated by escape — currently the only viable hypothesis — it had to be in the less unfamiliar context of Earth’s Archean atmosphere and under rather modest levels of EUV forcing. This requires a new model. Here we address the circumstances in which Xe, but not Kr, could escape from Earth as an ion. In a hydrodynamically escaping hydrogen wind the hydrogen is partially photo-ionized. The key concepts are that ions are much more strongly coupled to the escaping flow than are neutrals (so that a relatively modest flow of H and H+ to space could carry Xe+ along with it), and that xenon alone among the noble gases is more easily ionized than hydrogen. This sort of escape is possible if not prevented by a planetary magnetic field. The best prospects for Earth are therefore escape along the polar field lines, although a very weak or absent magnetic field would likely work as well. As applied to the Archean Earth the discussion will be constrained by diffusion-limited hydrogen escape. The extended history of hydrogen escape implicit in Xe escape in the Archean is consistent with suggestions that hydrogen escape from the anoxic Archean atmosphere was considerable, because biogenic methane is expected to have been rather abundant. Hydrogen escape plausibly played the key role in creating oxidizing condition at the surface of the Earth and setting the stage for the creation of an O2 atmosphere.

photo-ionized gases↗

Radiation GRMHD Models of Accretion onto Stellar-mass Black Holes. II. Super-Eddington Accretion

We present a comprehensive analysis of super-Eddington black hole accretion simulations that solve the GRMHD equations coupled with angle-discretized radiation transport. The simulations span a range of accretion rates, two black hole spins, and two magnetic field topologies, and include resolution studies as well as comparisons with nonradiative models. Super-Eddington accretion flows consistently develop geometrically thick disks supported by radiation pressure, regardless of magnetic field configuration. Radiation generated in the inner disk drives substantial outflows, forming conical funnel regions that limit photon escape and result in very low radiation efficiency. The accretion flows are highly turbulent, with thermal energy transport dominated by radiation advection rather than diffusion. Angular momentum is primarily carried outward by Maxwell stress, with turbulent Reynolds stress playing a subdominant role. Both strong and weak jets are produced. Strong jets arise from sufficient net vertical magnetic flux and rapid black hole spin, and they can effectively evacuate the funnel, enabling radiation to escape through strong geometric beaming. In contrast, weak jets fail to clear the funnel, which becomes obscured by radiation-driven outflows and leads to distinct observational signatures. Spiral structures are observed in the plunging region, behaving like density waves. These super-Eddington models are applicable to a variety of astronomical systems, including ultraluminous X-ray sources, little red dots, and black hole transients.

79 ASTRONOMY AND ASTROPHYSICS↗

Vertical transport and photochemistry in the terrestrial mesosphere and lower thermosphere /50-120 km/

A study is conducted of the coupled effects of kinetics, solar cycle flux variations, and vertical transport on the distribution of long-lived hydrogen-carbon-oxygen compounds in the terrestrial mesosphere and lower thermosphere, using a one-dimensional aeronomy model. The calculations account for the important chemical reactions and use rocket measurements of the solar flux at solar minimum and maximum. Photodissociation rates appropriate for the mesosphere are determined with a spherical shell atmosphere formalism. Detailed corrections for the O2 Schumann-Runge bands and the temperature dependence of the CO2 cross sections are used. An eddy diffusion profile is derived which is in agreement with the Aladdin 74 mass spectral measurements of atomic O, O2, CO2, and Ar in the lower thermosphere and observations of the O3 minimum at about 80 km.

Allen, M.↗

Quantitative analysis of ice films by near-infrared spectroscopy

One of the outstanding problems in the Space Transportation System is the possibility of the ice buildup on the external fuel tank surface while it is mounted on the launch pad. During the T-2 hours (and holding) period, the frost/ice thickness on the external tank is monitored/measured. However, after the resumption of the countdown time, the tank surface can only be monitored remotely. Currently, remote sensing is done with a TV camera coupled to a thermal imaging device. This device is capable of identifying the presence of ice, especially if it is covered with a layer of frost. However, it has difficulty identifying transparent ice, and, it is not capable of determining the thickness of ice in any case. Thus, there is a need for developing a technique for measuring the thickness of frost/ice on the tank surface during this two hour period before launch. The external tank surface is flooded with sunlight (natural or simulated) before launch. It may be possible, therefore, to analyze the diffuse reflection of sunlight from the external tank to determine the presence and thickness of ice. The purpose was to investigate the feasibility of this approach. A near-infrared spectrophotometer was used to record spectra of ice. It was determined that the optimum frequencies for monitoring the ice films were 1.03 and 1.255 microns.

Keiser, Joseph T.↗

Superconducting Nb DHEB Mixer Arrays for Far-Infrared Spectroscopy

We are developing a heterodyne focal plane array with up to eight elements to study lines of the interstellar medium and planetary atmospheres with frequencies of 2 THz and above. Our fabrication process utilizes selective ion milling techniques to produce Nb Diffusion-Cooled Hot Electron Bolometric (DHEB) mixers from a bilayer thin film of Au/Nb deposited on a silicon substrate. A micro-bridge of 10 nm thick Nb forms the HEB device. The first generation of devices with lateral dimensions of 100 nm by 80 nm were fabricated at the feed of a broadband spiral antenna with a frequency response designed for up to 16 THz. Harmonic multiplier sources becoming available within the next few years should have sufficient power to provide a local-oscillator source for small-format, quasi-optically coupled arrays of these mixers. First generation devices measured at our laboratory have demonstrated a critical temperature (Tc) of 4.8 K with a 0.5 K transition width. These DHEB mixers are expected to have an optimum operational temperature of 1.8-2.0 K. The current four element array mixer block will ultimately be replaced by a dual polarization slot-ring array configuration with up to eight elements.

Gerecht, E.↗

Pulsed Electromagnetic Acceleration of Plasmas

A major shift in paradigm in driving pulsed plasma thruster is necessary if the original goal of accelerating a plasma sheet efficiently to high velocities as a plasma "slug" is to be realized. Firstly, the plasma interior needs to be highly collisional so that it can be dammed by the plasma edge layer not (upstream) adjacent to the driving 'vacuum' magnetic field. Secondly, the plasma edge layer needs to be strongly magnetized so that its Hall parameter is of the order of unity in this region to ensure excellent coupling of the Lorentz force to the plasma. Thirdly, to prevent and/or suppress the occurrence of secondary arcs or restrike behind the plasma, the region behind the plasma needs to be collisionless and extremely magnetized with sufficiently large Hall parameter. This places a vacuum requirement on the bore conditions prior to the shot. These requirements are quantified in the paper and lead to the introduction of three new design parameters corresponding to these three plasma requirements. The first parameter, labeled in the paper as gamma (sub 1), pertains to the permissible ratio of the diffusive excursion of the plasma during the course of the acceleration to the plasma longitudinal dimension. The second parameter is the required Hall parameter of the edge plasma region, and the third parameter the required Hall parameter of the region behind the plasma. Experimental research is required to quantify the values of these design parameters. Based upon fundamental theory of the transport processes in plasma, some theoretical guidance on the choice of these parameters are provided to help designing the necessary experiments to acquire these data.

Thio, Y. C. Francis↗

Interfacial Hydrogen-Bond Dynamics in Transition Metal Compounds

Understanding how water behaves when confined within atomic layers of active transition-metal carbides, nitrides, and carbonitrides is essential for uncovering the fundamental principles needed to engineer solid–liquid interfaces at the atomic scale. Yet, how lattice element chemistry and surface termination groups collectively regulate the structure and mobility of such interlayer water remains poorly understood. Here, we present a composition-controlled investigation of interlayer water dynamics in layered transition-metal nitride, carbide, and carbonitride systems using a systematic integration of quasi-elastic neutron scattering (QENS), ab initio molecular dynamics (AIMD) simulations, and density functional theory (DFT) calculations. QENS measurements show that nitride-rich systems host mobile, translationally diffusing water with thermally activated self-diffusion coefficients on the order of 10 –10 m 2 s –1 , whereas mixed C/N lattices confine water to localized, nontranslational motion that is insensitive to temperature. AIMD and DFT reveal that lattice C/N chemistry and surface functional group composition reshape the first hydration layer by modulating the surface electronic structure and termination-dependent hydrogen-bond networks, leading to pronounced differences in water ordering and thermal resilience. On the other hand, fully carbide systems exhibit intermediate behavior, highlighting that water mobility is not primarily controlled by the hydration level alone but by the coupling between lattice composition and surface chemistry. Overall, this study establishes how surface chemistry and lattice composition jointly control interfacial hydrogen bond dynamics, offering a mechanistic framework for designing transition-metal layered materials with tailored interfacial transport properties.

Hydration↗

Dynamics of superconducting qubit relaxation times

Superconducting qubits are a leading candidate for quantum computing but display temporal fluctuations in their energy relaxation times T 1 . This introduces instabilities in multi-qubit device performance. Furthermore, autocorrelation in these time fluctuations introduces challenges for obtaining representative measures of T 1 for process optimization and device screening. These T 1 fluctuations are often attributed to time varying coupling of the qubit to defects, putative two level systems (TLSs). In this work, we develop a technique to probe the spectral and temporal dynamics of T 1 in single junction transmons by repeated T 1 measurements in the frequency vicinity of the bare qubit transition, via the AC-Stark effect. Across 10 qubits, we observe strong correlations between the mean T 1 averaged over approximately nine months and a snapshot of an equally weighted T 1 average over the Stark shifted frequency range. These observations are suggestive of an ergodic-like spectral diffusion of TLSs dominating T 1 , and offer a promising path to more rapid T 1 characterization for device screening and process optimization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗