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At least 397 records · Page 22

Spectroscopy of Exoplanet Atmospheres with the FINESSE Explorer

FINESSE (Fast INfrared Exoplanet Spectroscopic Survey Explorer) will provide uniquely detailed information on the growing number of newly discovered planets by characterizing their atmospheric composition and temperature structure. This NASA Explorer mission, selected for a competitive Phase A study, is unique in its breath and scope thanks to broad instantaneous spectroscopy from the optical to the mid-IR (0.7 - 5 micron), with a survey of exoplanets measured in a consistent, uniform way. For 200 transiting exoplanets ranging from Terrestrial to Jovians, FINESSE will measure the chemical composition and temperature structure of their atmospheres and trace changes over time with exoplanet longitude. The mission will do so by measuring the spectroscopic time series for a primary and secondary eclipse over the exoplanet orbital phase curve. With spectrophotometric precision being a key enabling aspect for combined light exoplanet characterization, FINESSE is designed to produce spectrophotometric precision of better than 100 parts-per-million per spectral channel without the need for decorrelation. The exceptional stability of FINESSE will even allow the mission to characterize non-transiting planets, potentially as part of FINESSE's Participating Scientist Program. In this paper, we discuss the flow down from the target availability to observations and scheduling to the analysis and calibration of the data and how it enables FINESSE to be the mission that will truly expand the new field of comparative exoplanetology.

chemical abundance↗

Reactive Extrusion of Waste Plastics with Compatibilizer and Lightly Pyrolyzed Crumb Rubber for Asphalt Modification

Modifying asphalt is a potentially high-value application for reusing waste plastics because of the high-volume usage of asphalt in highway construction. However, simply blending hot plastics and asphalt encounters difficulties related to the poor solubility of polymers, which limits the formation of a swollen network with asphalt molecules. The polymer phases also tend to coalesce and separate from asphalt during high-temperature storage in static conditions. The present study developed an innovative process to stabilize waste plastics in asphalt and improve binder storage stability by using lightly pyrolyzed crumb rubber together with a chemical compatibilizer. Both polymers were extruded to produce a thermoplastic elastomer (TPE) for asphalt modification. The mechanical performance and chemical reactions of TPEs were characterized via tension test and Fourier transform infrared spectroscopy. The storage stability and rheological properties of modified binder blends were evaluated through laboratory asphalt stability test and dynamic shear rheometer test. Polymer phases and network structures were characterized through optical microscopy. It was found that the pyrolyzed and reactive extrusion process improved the rubber solubility and polymer interaction, and therefore the storage stability of modified binder blends. The co-existence of rigid plastic and soft rubbery regimes in an entangled network provided a promising pathway to improve the mechanical performance of asphalt binders in both high- and low-temperature domains.

Ma, Yuetan↗

A Study of Strong Stability of Distributed Systems

The strong stability of distributed systems is studied and the problem of characterizing strongly stable semigroups of operators associated with distributed systems is addressed. Main emphasis is on contractive systems. Three different approaches to characterization of strongly stable contractive semigroups are developed. The first one is an operator theoretical approach. Using the theory of dilations, it is shown that every strongly stable contractive semigroup is related to the left shift semigroup on an L(exp 2) space. Then, a decomposition for the state space which identifies strongly stable and unstable states is introduced. Based on this decomposition, conditions for a contractive semigroup to be strongly stable are obtained. Finally, extensions of Lyapunov's equation for distributed parameter systems are investigated. Sufficient conditions for weak and strong stabilities of uniformly bounded semigroups are obtained by relaxing the equivalent norm condition on the right hand side of the Lyanupov equation. These characterizations are then applied to the problem of feedback stabilization. First, it is shown via the state space decomposition that under certain conditions a contractive system (A,B) can be strongly stabilized by the feedback -B(*). Then, application of the extensions of the Lyapunov equation results in sufficient conditions for weak, strong, and exponential stabilizations of contractive systems by the feedback -B(*). Finally, it is shown that for a contractive system, the first derivative of x with respect to time = Ax + Bu (where B is any linear bounded operator), there is a related linear quadratic regulator problem and a corresponding steady state Riccati equation which always has a bounded nonnegative solution.

Cataltepe, Tayfun↗

From bulk to surface: Structure and dynamics of amorphous alumina from deep potential molecular dynamics

Understanding the atomic-scale structure and dynamics of amorphous oxide surfaces is essential for interpreting their chemical reactivity, mechanical stability, and interfacial behavior, yet direct experimental characterization remains challenging. We employ Deep Potential (DP) molecular dynamics to generate large-scale, ab initio -quality models of amorphous Al 2 O 3 bulk glasses and melt-quenched free surfaces, enabling a quantitative analysis of both structure and relaxation dynamics with statistical confidence inaccessible to direct ab initio simulation. The trained DP model reproduces experimental liquid and glass structure, captures the cooling-rate dependence of the bulk glass transition, and corrects systematic biases in the polyhedral populations predicted by widely used classical force fields. At the free surface, mass density recovers to bulk values over ~10 Å, while local coordination requires a slightly wider subsurface region to fully converge. The outermost layer is oxygen-enriched, exhibits altered polyhedral connectivity with contracted Al–O bonds, and hosts a broad population of under-coordinated motifs (notably AlO 3 and OAl 2 ) whose abundances are governed by glass stability. These under-coordinated surface motifs exhibit distinct vibrational signatures and occur as locally paired Lewis acid and Brønsted base sites consistent with bond-valence compensation, yet remain spatially dispersed rather than aggregating into extended clusters. Despite this pronounced structural heterogeneity, surface relaxation and the glass-transition temperature remain comparable to their bulk counterparts, suggesting that the disordered surface is kinetically stable once formed. Together, these results establish a molecular-level picture of amorphous alumina surfaces and demonstrate the capability of machine-learned potentials to resolve structure–property relationships in disordered oxide interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controller synthesis for infinite dimensional systems based on a passivity approach

The author discusses a generalization of hyperstability to systems in Hilbert space and its application to finite-dimensional stabilizing compensator design. The basic idea is to characterize tolerable perturbations in terms of the passivity of the nominal closed-loop system. Controllers achieving the required closed-loop passivity property can then be designed using H(infinity)-optimization. In particular, the author presents a design procedure for a stabilizing a finite-dimensional compensator for a given infinite-dimensional system.

Wen, John T.↗

The onset of electrohydrodynamic instability in isoelectric focusing

The onset of electrohydrodynamic motion associated with the imposition of an electric field across a thin layer of liquid has been investigated for the case in which the electrical conductivity varies linearly over the depth of the layer. The variation of the conductivity is due to concentration gradients in the charge-carrying solutes and its spatio-temporal evolution is represented by a convective-diffusion equation. When the viscous relaxation time is long compared to the time for charge relaxation, the analysis reveals that the neutral stability curves for the layer can be characterized by three dimensionless parameters: Ra(sub e) is equivalent to d(epsilon)E(sup 2, sub 0) Delta sigma/mu K(sub eff) sigma(sub 0), an electrical Rayleigh number; delta sigma/sigma(sub 0), the relative conductivity increment; and alpha, the transverse wave number of the disturbance. Here d is the thickness, epsilon is the dielectric constant, and mu is the viscosity of layer, E(sub 0) is the applied field strength at the lower conductivity boundary, and K(sub eff) is an effective diffusivity associated with the Brownian motion of the charge-carrying solutes. With viscous-stress-free boundaries, at which the electrical conductivity and the normal component of the electric field are prescribed, the critical Ra(sub e) is 1.504 x 10(exp 4) at a critical transverse wave number of 1.97 when Delta sigma/sigma(sub 0) is 10. As Delta sigma/sigma(sub 0) increases, the critical Ra(sub e) increases and shifts to shorter wavelength disturbances; the critical imposed field strength, however, passes through a minimum because the lower-conductivity boundary exerts a considerable stabilizing influence in the presence of steep conductivity gradients. Similar trends were obtained for liquid layers with rigid boundaries.

Baygents, James C.↗

Commissioning the H i Observing Mode of the Beam Former for the Cryogenically Cooled Focal L-band Array for the GBT (FLAG)

We present the results of commissioning observations for a new digital beam-forming back end for the Focal plane L-band Array for the Robert C. Byrd Green Bank Telescope (FLAG), a cryogenically cooled Phased Array Feed (PAF) with the lowest measured T {sub sys}/η of any PAF outfitted on a radio telescope to date. We describe the custom software used to apply beam-forming weights to the raw element covariances to create research-quality spectral-line images for the new fine-channel mode, study the stability of the beam weights over time, characterize FLAG’s sensitivity over a frequency range of 150 MHz, and compare the measured noise properties and observed distribution of neutral hydrogen emission from several extragalactic and Galactic sources with data obtained with the current single-pixel L-band receiver. These commissioning runs establish FLAG as the preeminent PAF receiver currently available for spectral-line observations on the world’s major radio telescopes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Cu(II) Stability and UV-Induced Electron Transfer in a Metal–Organic Hybrid: An EPR, DFT, and Crystallographic Characterization of Copper-Doped Zinc Creatininium Sulfate

Single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopic experiments, complemented by quantum chemical DFT calculations, were carried out on the copper-doped metal–organic hybrid and Tutton salt analogue zinc creatininium sulfate to determine its crystal structure, to characterize the electronic structure of the doped Cu(II) binding site, and to propose a pathway for an excited-state, proton-coupled electron transfer (PCET) process in UV-exposed crystals. The crystal structure is isomorphous to that of cadmium creatininium sulfate, which has the transition ion, not in direct coordination with the creatinine, but forming a hexahydrate complex, which is bridged to a creatininium through an intervening sulfate ion. The EPR g (2.446, 2.112, 2.082) and copper hyperfine (A Cu : -327, -59.6, 10.8 MHz) tensor parameters are consistent with doped copper replacing host zinc in the metal–hexahydrate complex. These parameters are similar to those observed for copper hexahydrate in doped Tutton salt systems at low temperature, where the unpaired electron occupies mainly the copper 3d x 2 –y 2 orbital. At room temperature in the Tutton systems, vibration couplings stemming from a dynamic Jahn–Teller effect cause tensor averaging which results in a reduction in their maximum g-tensor and hyperfine tensor values. However, like for the doped isomorphous Cd creatinine crystal, the Cu(II) EPR exhibits little, or no room temperature averaging compared to its low temperature pattern. Samples exposed to 254 nm UV light generate a carbon-centered free radical species, characterized by an isotropic g-tensor (g = 2.0029) and an alpha-proton hyperfine coupling (-24 -14 +4 G). These parameters identify it as a creatinine radical cation formed by the oxidative release of one of its C2 methylene hydrogens. DFT calculations confirm the unpaired electronic structures of both the Cu(II) site and free radical. The growth in radical concentration with an increase in the UV exposure time coincides with a decrease in the copper EPR signal, indicating a coupled light-induced oxidation reduction process. A comparison of the crystal structure with the EPR parameters and DFT results provides evidence for a UV-induced PCET.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Soft x ray window encapsulant for HgI2 detectors

HgI2 is an excellent semiconductor material for a low energy, room temperature x-ray spectrometer. The high values of the atomic numbers for its constituent elements gives high x-ray and gamma ray stopping power. The band gap of HgI2 is significantly higher than other commonly used semiconductors. Owing to the large value band gap, the leakage current for HgI2 devices is smaller, thus allowing low noise performance. Devices fabricated from HgI2 crystals have demonstrated energy resolution sufficient to distinguish the x-ray emission from the neighboring elements on the periodic table. Also the power requirements of HgI2 are very low. These characteristics make a HgI2 spectrometer an ideal component in a satellite based detection system. Unfortunately, HgI2 crystals tend to deteriorate with time, even if protected by standard semiconductor encapsulants. This degradation ruins the performance of the device in terms of its energy resolution and pulse amplitude. The degrading mechanism is believed to be material loss occurring from below the electrodes, due to high vapor pressure of HgI2 at room temperature. To address this major obstacle to rapid expansion of HgI2 technology, a research program aimed at improving device stability by encapsulation with inert polymeric materials was carried out. The program focused specifically on optimizing the encapsulant materials and their deposition techniques. The principal objectives for this program were device encapsulation, device testing, and accelerated testing to ensure very long term stability of these high resolution sensors. A variety of encapsulants were investigated with the selection criteria based on their chemical diffusion barrier properties, mechanical stability, reactivity, and morphology of encapsulant films. The investigation covered different classes of encapsulants including solvent based encapsulants, vapor deposited encapsulants, and plasma polymerized encapsulants. A variety of characterization techniques were employed to examine their effectiveness in stabilizing HgI2 devices; these included permeability evaluation, vacuum and heat testing, scanning electron microscopy (SEM) as well as studying the detector performance of coated detectors. The plasma polymerized films appear to have entirely solved the HgI2 degradation problem. Another achievement of this program was the development of an accelerated testing technique which correlates extremely well with long term tesing.

Entine, G.↗

Summary of stability and control characteristics of the XB-70 airplane

The stability and control characteristics of the XB-70 airplane were evaluated for Mach numbers up to 3.0 and altitudes up to 21,300 meters (70,000 feet). The airplane's inherent longitudinal characteristics proved to be generally satisfactory. In the lateral-directional modes, the airplane was characterized by light wheel forces, low static directional stability beyond approximately 2 deg of sideslip, adverse yaw response to aileron inputs throughout the entire Mach number range, and negative effective dihedral with wingtips full down. At subsonic Mach numbers, with the flight augmentation control system off, the light wheel forces and adverse yaw response to aileron inputs caused the pilots to minimize use of the ailerons. At supersonic Mach numbers, with the augmentation system off, the adverse yaw due to aileron and the negative effective dihedral were conducive to pilot-induced oscillations.

Wolowicz, C. H.↗

Status of Gr/glass composites technology at UTOS

The TSC (Thermally Stable Composite) refers to a family of graphite reinforced glass matrix composite materials developed by UTOS. This fiber matrix combination exhibits low coefficients of thermal expansion (CTE), exceptional dimensional stability, high specific strength and stiffness, adequate fracture toughness, and space environment compatibility. The dimensional stability of a TSC mirror structure was experimentally characterized at the Steward Observatory. Preliminary results indicate that TSC is significantly more thermally stable than most current structural composite materials. In addition, the use of lower CTE glass matrix materials, such as 96 percent silica glass, have the potential for producing graphite/glass panels with expansion rates and stability comparable to that of fused silica.

Mayor, Ramon A.↗

A numerical study of global axisymmetric states and their stability to quasi-geostrophic disturbances

A steady, axisymmetric model of the general circulation is developed as a basis for climate stability studies. The model includes the effects of heating, rotation, and internal friction, but neglects topography. It is assumed that the axisymmetric flow may be modeled by making the Boussinesq and deep convection approximations. The hydrostatic assumption is not made, thus permitting the advective terms to be included in the vertical equation of motion. The initial set of five primitive equations is reduced to three equations in terms of the zonal velocity, meridional streamfunction, and the potential temperature perturbation. The application of the Boussinesq, deep convection, and quasi-geostrophic assumptions limits the ranges of the heating and rotation rates. For values not too far from typical atmospheric values, the model produces a stability boundary separating Hadley from Rossby flow. The boundary is characterized by a particular value of vertical wind shear, which suggests that baroclinic instability is the primary mechanism for the loss of stability. The initial growth rates are largest for longitudinal waves 4-7, also in agreement with studies of baroclinic instability.

Henderson, H. W.↗

Atomically Dispersed Dual‐Metal Site Catalysts for Enhanced CO 2 Reduction: Mechanistic Insight into Active Site Structures

Abstract Carbon‐supported nitrogen‐coordinated single‐metal site catalysts (i.e., M−N−C, M: Fe, Co, or Ni) are active for the electrochemical CO 2 reduction reaction (CO 2 RR) to CO. Further improving their intrinsic activity and selectivity by tuning their N−M bond structures and coordination is limited. Herein, we expand the coordination environments of M−N−C catalysts by designing dual‐metal active sites. The Ni‐Fe catalyst exhibited the most efficient CO2RR activity and promising stability compared to other combinations. Advanced structural characterization and theoretical prediction suggest that the most active N‐coordinated dual‐metal site configurations are 2N‐bridged (Fe‐Ni)N 6 , in which FeN 4 and NiN 4 moieties are shared with two N atoms. Two metals (i.e., Fe and Ni) in the dual‐metal site likely generate a synergy to enable more optimal *COOH adsorption and *CO desorption than single‐metal sites (FeN 4 or NiN 4 ) with improved intrinsic catalytic activity and selectivity.

Li, Yi↗

SEC ‐ SAXS / MC Ensemble Structural Studies of the Microtubule Binding Protein Cdt1 Show Monomeric, Folded‐Over Conformations

ABSTRACT Cdt1 is a mixed folded protein critical for DNA replication licensing and it also has a “moonlighting” role at the kinetochore via direct binding to microtubules and the Ndc80 complex. However, it is unknown how the structure and conformations of Cdt1 could allow it to participate in these multiple, unique sets of protein complexes. While robust methods exist to study entirely folded or unfolded proteins, structure–function studies of combined, mixed folded/disordered proteins remain challenging. In this work, we employ orthogonal biophysical and computational techniques to provide structural characterization of mitosis‐competent human Cdt1. Thermal stability analyses shows that both folded winged helix domains1 are unstable. CD and NMR show that the N‐terminal and linker regions are intrinsically disordered. DLS shows that Cdt1 is monomeric and polydisperse, while SEC‐MALS confirms that it is monomeric at high concentrations, but without any apparent inter‐molecular self‐association. SEC‐SAXS enabled computational modeling of the protein structures. Using the program SASSIE, we performed rigid body Monte Carlo simulations to generate a conformational ensemble of structures. We observe that neither fully extended nor extremely compact Cdt1 conformations are consistent with SAXS. The best‐fit models have the N‐terminal and linker disordered regions extended into the solution and the two folded domains close to each other in apparent “folded over” conformations. We hypothesize the best‐fit Cdt1 conformations could be consistent with a function as a scaffold protein that may be sterically blocked without binding partners. Our study also provides a template for combining experimental and computational techniques to study mixed‐folded proteins.

Cell Biology↗

Cross-scale modeling and experimental integration for advancing cathode electrolyte interphase studies in high energy density lithium-ion batteries

Electrochemical interfaces are critical to the performance and durability of lithium-ion batteries (LIBs). The solid electrode-electrolyte interphase (SEI and CEI) structures that form during cycling can passivate reactive surfaces, ensuring safe operation, but also may contribute to performance degradation. Understanding the microscopic factors influencing interphase formation, growth, and evolution is essential for balanced battery design. While significant research has focused on the anode-electrolyte interphase (SEI), the cathode-electrolyte interphase (CEI) remains less explored, despite its importance in high-voltage and advanced battery technologies. Challenges in conducting in-situ or operando experiments arise from the occluded nature of these interfaces and the long timescales involved, often leading to biased interpretations. A validated multi-scale, multi-physics modeling approach, integrated with advanced characterization techniques, can effectively elucidate the intrinsic stability of electrolyte and cathode surfaces, the impact of chemical heterogeneity, and the role of microstructural features on CEI performance. In conclusion, this article reviews current modeling and simulation strategies for studying CEI in advanced LIBs and highlights opportunities for future methodological advancements and experimental integration.

Cathode-electrolyte interphase↗

Learning interpretable surface elasticity properties from bulk properties via neural network equation learners

Surface elasticity is central to understanding the mechanics and stability of surfaces and interfaces. It is characterized by quantities such as surface tension, residual surface stress, and surface stiffness. However their analytical expressions are typically difficult to derive from atomistic data, and depend strongly on modeling choices. This work presents a neural network-based equation learner which combines customized activation functions and connection-based pruning to discover parsimonious, closed-form equations for surface elasticity from atomistic simulations. Applying the method to seven face-centered cubic (FCC) metals, our equation learner uncovers interpretable equations that describe both low-Miller index and high-Miller index surface properties, capturing long-tail property distributions accurately. The discovered expressions are decoupled into two components: a universal, geometry-driven orientation function, and material-specific baseline coefficients. We find that lower-order properties such as surface tension are fundamentally geometry dependent, while higher-order properties such as surface stress and elasticity show more complex geometry and material dependence. We also relate material dependent coefficients to bulk properties, forming a clear map from bulk material properties to surface elasticity. Overall, this approach demonstrates that interpretable neurosymbolic machine learning can bridge the gap between atomistic simulations and physical laws, enabling the discovery of generalizable structure–property relationships for materials science phenomena such as surface elasticity.

Equation learning↗

Engineered MXene quantum dots for micro-supercapacitors with excellent capacitive behaviors

Micro-supercapacitors (MSCs) have drawn tremendous attention as promising candidates to power miniaturized portable/wearable electronics, but they still suffer from unsatisfactory electrochemical performance (e.g., insufficient energy density, mediocre rate capability), thus impeding their widespread applications. Here, a synergistic surface and structure engineering strategy achieved by downsizing to quantum dot scale, doping of heteroatoms, and introducing defects and functional groups is proposed to regulate the physicochemical properties of Ti 3 C 2 T x MXene. Encouragingly, the resulting MSCs based on defect-rich nitrogen-doped Ti 3 C 2 T x quantum dots (QDs) possess excellent electrochemical performance as demonstrated by large operating voltage (3.0 V in ionic liquid and 1.0 V in aqueous electrolyte), perfect rectangular CV shape even at 1000 V·s -1 , high volumetric capacitance of 33.1 F·cm -3 , and superior cycling stability after 10000 cycles. By employing experimental characterizations and density functional theory calculations, the remarkable performance of the MSCs is mainly due to the special chemical states as well as the unique surface and structural features of Ti 3 C 2 T x QDs, which offer abundant active sites, shorten ion diffusion pathways, promote ion/electron transports, and provide enhanced capacitance. Finally, this work provides a new strategy for the design of high-performance MSCs and a reference for the applications of MXene QDs in other energy-related fields.

42 ENGINEERING↗

Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

The application of bimolecular reductive elimination to the activation of iron catalysts for alkene–diene cycloaddition is described. Key to this approach was the synthesis, characterization, electronic structure determination, and ultimately solution stability of a family of pyridine(diimine) iron methyl complexes with diverse steric properties and electronic ground states. Both the aryl-substituted, ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 ( R PDI = 2,6-(2,6-R 2 -C 6 H 3 N=CMe) 2 C 5 H 3 N), and the alkyl-substituted examples, ( Cy APDI)FeCH 3 ( Cy APDI = 2,6-(C 6 H 11 N=CMe) 2 C 5 H 3 N), have molecular structures significantly distorted from planarity and S = 3/2 ground states. The related N-arylated derivative bearing 2,6-di-isopropyl aryl substituents, ( iPr PDI)FeCH 3 , has an idealized planar geometry and exhibits spin crossover behavior from S = 1/2 to S = 3/2 states. At 23 °C under an N 2 atmosphere, both ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 underwent reductive elimination of ethane to form the iron dinitrogen precatalysts, [( Me PDI)Fe(N 2 )] 2 (μ-N 2 ) and [( Et PDI)Fe(N 2 )] 2 (μ-N 2 ), respectively, while ( iPr PDI)FeCH 3 proved inert to C–C bond formation. By contrast, addition of butadiene to all three iron methyl complexes induced ethane formation and generated the corresponding iron butadiene complexes, ( R PDI)Fe(η 4 -C 4 H 6 ) (R = Me, Et, i Pr), known precatalysts for the [2+2] cycloaddition of olefins and dienes. Kinetic, crossover experiments, and structural studies were combined with magnetic measurements and Mössbauer spectroscopy to elucidate the electronic and steric features of the iron complexes that enable this unusual reductive elimination and precatalyst activation pathway. Furthermore, transmetalation of methyl groups between iron centers was fast at ambient temperature and independent of steric environment or spin state, while the intermediate dimer underwent the sterically controlled rate-determining reaction with either N 2 or butadiene to access a catalytically active iron compound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗