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At least 127 records · Page 7

Synthesis of carbon core–shell pore structures and their performance as supercapacitors

High-power supercapacitors require excellent electrolyte mobility within the pore network and high electrical conductivity for maximum capacitance and efficiency. Achieving high power typically requires sacrificing energy densities, as the latter demands a high specific surface area and narrow porosity that impedes ion transport. Here, we present a novel solution for this optimization problem: a nanostructured core–shell carbonaceous material that exhibits a microporous carbon core surrounded by a mesoporous, graphitic shell. The tunable synthesis parameters yielded a structure that features either a sharp or a gradual transition between the core and shell sections. Electrochemical supercapacitor testing using organic electrolyte revealed that these novel core–shell materials outperform carbons with homogeneous pore structures. The hybrid core–shell materials showed a combination of good capacitance retention, typical for the carbon present in the shell and high specific capacitance, typical for the core material. These materials achieved power densities in excess of 40 kW kg -1 at energy densities reaching 27 Wh kg -1 .

25 ENERGY STORAGE↗

Conversion between triplet pair states is controlled by molecular coupling in pentadithiophene thin films

In singlet fission (SF) the initially formed correlated triplet pair state, 1 (TT), may evolve toward independent triplet excitons or higher spin states of the (TT) species. The latter result is often considered undesirable from a light harvesting perspective but may be attractive for quantum information sciences (QIS) applications, as the final exciton pair can be spin-entangled and magnetically active with relatively long room temperature decoherence times. In this study we use ultrafast transient absorption (TA) and time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy to monitor SF and triplet pair evolution in a series of alkyl silyl-functionalized pentadithiophene (PDT) thin films designed with systematically varying pairwise and long-range molecular interactions between PDT chromophores. The lifetime of the (TT) species varies from 40 ns to 1.5 μs, the latter of which is associated with extremely weak intermolecular coupling, sharp optical spectroscopic features, and complex TR-EPR spectra that are composed of a mixture of triplet and quintet-like features. On the other hand, more tightly coupled films produce broader transient optical spectra but simpler TR-EPR spectra consistent with significant population in 5 (TT) 0 . These distinctions are rationalized through the role of exciton diffusion and predictions of TT state mixing with low exchange coupling J versus pure spin substate population with larger J. The connection between population evolution using electronic and spin spectroscopies enables assignments that provide a more detailed picture of triplet pair evolution than previously presented and provides critical guidance for designing molecular QIS systems based on light-induced spin coherence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new approach to enforcing discrete maximum principles in continuous Galerkin methods for convection-dominated transport equations

This work introduces a set of design principles and new algorithmic tools for enforcing maximum principles and/or positivity preservation in continuous finite element approximations to convection-dominated transport problems. Enabling a linear first-order advection equation as a model problem, we address the design of first-order artificial diffusion operators and their higherorder counterparts at the element matrix level. The proposed methodology leads to a nonlinear high-resolution scheme capable of resolving moving fronts and internal/boundary layers as sharp localized nonoscillatory features. The amount of numerical dissipation depends on the difference between the solution value at a given node and a local maximum or minimum. The shockcapturing numerical diffusion coefficient is designed to vanish as the nodal values approach a mass-weighted or linearity-preserving average. The universal applicability and simplicity of the element-based limiting procedure makes it an attractive alternative to edge-based algebraic flux correction.

Kuzmin, D.↗

Nature of exciton transitions in hexagonal boron nitride

In contrast to other III-nitride semiconductors GaN and AlN, the intrinsic (or free) exciton transition in hexagonal boron nitride ( h -BN) consists of rather complex fine spectral features (resolved into six sharp emission peaks) and the origin of which is still unclear. In this work, the free exciton transition (FX) in h -BN bulk crystals synthesized by a solution method at atmospheric pressure has been probed by deep UV time-resolved photoluminescence (PL) spectroscopy. Based on the separations between the energy peak positions of the FX emission lines, the identical PL decay kinetics among different FX emission lines, and the known phonon modes in h -BN, we suggest that there is only one principal emission line corresponding to the direct intrinsic FX transition in h -BN, whereas all other fine features are a result of phonon-assisted transitions. The identified phonon modes are all associated with the center of the Brillouin zone. Our results offer a simple picture for the understanding of the fundamental exciton transitions in h -BN.

36 MATERIALS SCIENCE↗

Synergistic ground and orbital observations of iron oxides on Mt. Sharp and Vera Rubin ridge

Visible/short-wave infrared spectral data from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) show absorptions attributed to hematite at Vera Rubin ridge (VRR), a topographic feature on northwest Mt. Sharp. The goals of this study are to determine why absorptions caused by ferric iron are strongly visible from orbit at VRR, and to improve interpretation of CRISM data throughout lower Mt. Sharp. These goals are achieved by analyzing coordinated CRISM and in situ spectral data along the Curiosity Mars rover’s traverse. VRR bedrock within areas that have the deepest ferric absorptions in CRISM data also have the deepest ferric absorptions measured in situ. This suggests strong ferric absorptions are visible from orbit at VRR because of the unique spectral properties of VRR bedrock. Dust and mixing with basaltic sand additionally inhibit the ability to measure ferric absorptions in bedrock stratigraphically below VRR from orbit. There are two implications of these findings: (1) Ferric absorptions in CRISM data initially dismissed as noise could be real, and ferric phases are more widespread in lower Mt. Sharp than previously reported, (2) Patches with the deepest ferric absorptions in CRISM data are, like VRR, reflective of deeper absorptions in the bedrock. One model to explain this spectral variability is late-stage diagenetic fluids that changed the grain size of ferric phases, deepening absorptions. Curiosity’s experience highlights the strengths of using CRISM data for spectral absorptions and associated mineral detections, and the caveats in using these data for geologic interpretations and strategic path planning tools.

58 GEOSCIENCES↗

Combined features in the primordial spectra induced by a sudden turn in two-field DBI inflation

We investigate the features generated by a sharp turn along the inflationary trajectory in a two-field model of Dirac-Born-Infeld inflation, where one of the fields is heavy. Distinct features are generated by two different effects: the mixing of the light and heavy modes during the turn, on the one hand, and the resonance between the oscillations along the heavy direction after the turn, on the other hand. Contrary to models with standard kinetic terms, the resonance effect is not strongly suppressed because the action contains derivative interactions. Working in the potential basis, we study the oscillations after the turn and compute the amplitude of the mixing and resonance features in the power spectrum, as well as in the bispectrum for the latter effect. We find that the amplitudes and positions of these combined features obey specific consistency relations, which could be confronted with cosmological data.

79 ASTRONOMY AND ASTROPHYSICS↗

Novel gamma-ray spectral features in the inert doublet model

The inert doublet model contains a neutral stable particle which is an excellent dark matter candidate. We discuss in this paper the indirect signatures of this model in gamma-rays when the dark matter mass is larger than the W boson mass. We show that, in addition to the featureless gamma-ray spectrum produced in the annihilations into two weak gauge bosons, the model generically predicts a distinctive spectral feature from the internal bremsstrahlung process H{sup 0}H{sup 0}→W{sup +}W{sup −}γ. We discuss under which conditions the spectral feature is generated and we construct a number of benchmark points, compatible with the observed relic density and all other direct and indirect detection experiments, which lead to a sharp gamma-ray feature from internal bremsstrahlung.

79 ASTRONOMY AND ASTROPHYSICS↗

Use of carbonyldiimidazole as a derivatization agent for the detection of pinacolyl alcohol, a forensic marker for Soman, by EI-GC–MS and LC-HRMS in official OPCW proficiency test matrices

Pinacolyl alcohol (PA), a key forensic marker for the nerve agent Soman (GD), is a particularly difficult analyte to detect by various analytical methods. In this work, we have explored the reaction between PA and 1,1'-carbonyldiimidazole (CDI) to yield pinacolyl 1H-imidazole-1-carboxylate (PIC), a product that can be conveniently detected by gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS). Regarding its GC–MS profile, this new carbamate derivative of PA possesses favorable chromatographic features such as a sharp peak and a longer retention time (RT = 16.62 min) relative to PA (broad peak and short retention time, RT = 4.1 min). Additionally, the derivative can also be detected by LC-HRMS, providing an avenue for the analysis of this chemical using this technique where PA is virtually undetectable unless present in large concentrations. From a forensic science standpoint, detection of this low molecular weight alcohol signals the past or latent presence of the nerve agent Soman (GD) in a given matrix (i.e., environmental or biological). The efficiency of the protocol was tested separately in the analysis and detection of PA by EI-GC–MS and LC-HRMS when present at a 10 μg/mL in a soil matrix featured in the 44th PT and in a glycerol-rich liquid matrix featured in the 48th Official Organization for the Prohibition of Chemical Weapons (OPCW) Proficiency Test when present at a 5 μg/mL concentration. In both scenarios, PA was successfully transformed into PIC, establishing the protocol as an additional tool for the analysis of this unnatural and unique nerve agent marker by GC–MS and LC-HRMS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting laser weld reliability with stochastic reduced-order models. Predicting laser weld reliability

Laser welds are prevalent in complex engineering systems and they frequently govern failure. The weld process often results in partial penetration of the base metals, leaving sharp crack-like features with a high degree of variability in the geometry and material properties of the welded structure. Furthermore, accurate finite element predictions of the structural reliability of components containing laser welds requires the analysis of a large number of finite element meshes with very fine spatial resolution, where each mesh has different geometry and/or material properties in the welded region to address variability. We found that traditional modeling approaches could not be efficiently employed. Consequently, a method is presented for constructing a surrogate model, based on stochastic reduced-order models, and is proposed to represent the laser welds within the component. Here, the uncertainty in weld microstructure and geometry is captured by calibrating plasticity parameters to experimental observations of necking as, because of the ductility of the welds, necking – and thus peak load – plays the pivotal role in structural failure. The proposed method is exercised for a simplified verification problem and compared with the traditional Monte Carlo simulation with rather remarkable results.

36 MATERIALS SCIENCE↗

Carbon Monoxide Mediated Hydrogen Release from PtCu Single-Atom Alloys: The Punctured Molecular Cork Effect

Pt-based materials are used extensively in heterogeneous catalytic processes, yet they are notoriously susceptible to poisoning by CO. In contrast, highly dilute binary alloys formed of isolated Pt atoms in a Cu metal host, known as PtCu single-atom alloys (SAAs), are more resilient to CO poisoning during catalytic hydrogenation reactions. In this article, we describe how CO affects the adsorption and desorption of H 2 from a model PtCu(111) SAA surface and gain a microscopic understanding of these species’ interaction at the Pt atom active sites. By combining temperature-programmed desorption and scanning tunneling microscopy with first-principles kinetic Monte Carlo, we identify CO as a Pt site blocker that prevents the low temperature adsorption and desorption of H 2 , the so-called molecular cork effect , first realized when examining PdCu SAAs. Intriguingly, for the case of PtCu, H 2 desorption occurs before CO release is detected. Additionally, desorption experiments show a nonlinear relationship between CO coverage of the Pt sites and H 2 desorption peak temperature. When all the Pt atoms are saturated by CO, a very sharp H 2 desorption feature is observed 55 K above the regular desorption temperature of H 2 . Our simulations reveal that the origin of these effects is the fact that desorption of just one CO molecule from a Pt site facilitates the fast release of many molecules of H 2 . In fact, just 0.7% of the CO adsorbed at Pt sites has desorbed when the H 2 desorption peak maximum is reached. The release of H 2 from CO-corked PtCu SAA surfaces is analogous to the escape of gas from a pressurized container with a small puncture. Given that small changes in CO surface coverage lead to large changes in H 2 evolution energetics, the punctured molecular cork effect must be considered when modeling reaction mechanisms on similar alloy systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization

Lithium (Li) pulverization and associated large volume expansion during cycling is one of the most critical barriers for the safe operation of Li-metal batteries. Here, we report an approach to minimize the Li pulverization using an electrolyte based on a fluorinated orthoformate solvent. The solid–electrolyte interphase (SEI) formed in this electrolyte clearly exhibits a monolithic feature, which is in sharp contrast with the widely reported mosaic- or multilayer-type SEIs that are not homogeneous and could lead to uneven Li stripping/plating and fast Li and electrolyte depletion over cycling. The highly homogeneous and amorphous SEI not only prevents dendritic Li formation, but also minimizes Li loss and volumetric expansion. Furthermore, this new electrolyte strongly suppresses the phase transformation of the LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode (from layered structure to rock salt) and stabilizes its structure. In conclusion, tests of high-voltage Li||NMC811 cells show long-term cycling stability and high rate capability, as well as reduced safety concerns.

25 ENERGY STORAGE↗

Dynamic Fano-like resonances in erbium-doped whispering-gallery-mode microresonators

We report Fano-like asymmetric resonances modulated by optical gain in a whispering-gallery-mode resonator fabricated from erbium-doped silica. A time-dependent gain profile leads to dynamically varying sharp asymmetric resonances with features similar to Fano resonances. Depending on the scan speed of the frequency of the probe laser and the pump-probe power ratio, transmission spectra of the active microcavity exhibit a resonance dip, a resonance peak, or a Fano-like resonance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Scalar dark matter models with significant internal bremsstrahlung

There has been interest recently on particle physics models that may give rise to sharp gamma ray spectral features from dark matter annihilation. Because dark matter is supposed to be electrically neutral, it is challenging to build weakly interacting massive particle models that may accommodate both a large cross section into gamma rays at, say, the Galactic center, and the right dark matter abundance. In this work, we consider the gamma ray signatures of a class of scalar dark matter models that interact with Standard Model dominantly through heavy vector-like fermions (the vector-like portal). We focus on a real scalar singlet S annihilating into lepton-antilepton pairs. Because this two-body final-state annihilation channel is d-wave suppressed in the chiral limit, σ{sub ff-bar}v∝v{sup 4}, we show that virtual internal bremsstrahlung emission of a gamma ray gives a large correction, both today and at the time of freeze-out. For the sake of comparison, we confront this scenario to the familiar case of a Majorana singlet annihilating into light lepton-antilepton pairs, and show that the virtual internal bremsstrahlung signal may be enhanced by a factor of (up to) two orders of magnitude. We discuss the scope and possible generalizations of the model.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Modelling a Transition-Edge Sensor X-Ray Microcalorimeter Linear Array for Compton Profile Measurements and Energy Dispersive Diffraction

Transition-edge sensors (TES) are a type of superconducting detector that offers high energy resolution based on their sharp resistance-temperature feature in the superconducting-to-normal transition. TES X-ray microcalorimeters have typically been designed and used for spectroscopic applications. In this work, we present a design optimization for a TES X-ray microcalorimeter array for high-energy scattering and diffraction measurements. Specifically, Compton scattering provides information about the electron momentum distribution, while energy dispersive diffraction provides structural information about dense engineering materials. Compton scattering and energy dispersive diffraction experiments must be conducted in the very hard X-ray regime (~100 keV), demanding a high X-ray stopping power in the detector; therefore, an absorber with a large heat capacity is needed in conjunction with the TES. In addition, both applications would benefit from an array composed of parallel strips. We propose a design for a TES X-ray microcalorimeter optimized for such applications. In particular, we model the longitudinal position dependence due to the finite thermal diffusion time in the absorber.

47 OTHER INSTRUMENTATION↗

Low-Level Mesoscale and Cloud-Scale Interactions Promoting Deep Convection Initiation

Data from scanning radars, radiosondes, and vertical profilers deployed during three field campaigns are analyzed to study interactions between cloud-scale updrafts associated with initiating deep moist convection and the surrounding environment. Three cases are analyzed in which the radar networks permitted dual-Doppler wind retrievals in clear air preceding and during the onset of surface precipitation. These observations capture the evolution of (i) the mesoscale and boundary layer flow, and (ii) low-level updrafts associated with deep moist convection initiation (CI) events yielding sustained or short-lived precipitating storms. The elimination of convective inhibition did not distinguish between sustained and unsustained CI events, though the vertical distribution of convective available potential energy may have played a role. The clearest signal differentiating the initiation of sustained versus unsustained precipitating deep convection was the depth of the low-level horizontal wind convergence associated with the mesoscale flow feature triggering CI, a sharp surface wind shift boundary, or orographic upslope flow. The depth of the boundary layer relative to the height of the LFC failed to be a consistent indicator of CI potential. Widths of the earliest detectable low-level updrafts associated with sustained precipitating deep convection were ~3–5 km, larger than updrafts associated with surrounding boundary layer turbulence (~1–3 km wide). It is hypothesized that updrafts of this larger size are important for initiating cells to survive the destructive effects of buoyancy dilution via entrainment.

54 ENVIRONMENTAL SCIENCES↗

M-Edge Spectroscopy of Transition Metals: Principles, Advances, and Applications

M-edge X-ray absorption spectroscopy (XAS), which probes 3p→3d transitions in first-row transition metals, provides detailed insights into oxidation states, spin-states, and local electronic structure with high element and orbital specificity. Operating in the extreme ultraviolet (XUV) region, this technique provides sharp multiplet-resolved features with high sensitivity to ligand field and covalency effects. Compared to K- and L-edge XAS, M-edge spectra exhibit significantly narrower full widths at half maximum (typically 0.3–0.5 eV versus >1 eV at the L-edge and >1.5–2 eV at the K-edge), owing to longer 3p core-hole lifetimes. M-edge measurements are also more surface-sensitive due to the lower photon energy range, making them particularly well-suited for probing thin films, interfaces, and surface-bound species. The advent of tabletop high-harmonic generation (HHG) sources has enabled femtosecond time-resolved M-edge measurements, allowing direct observation of ultrafast photoinduced processes such as charge transfer and spin crossover dynamics. This review presents an overview of the fundamental principles, experimental advances, and current theoretical approaches for interpreting M-edge spectra. We further discuss a range of applications in catalysis, materials science, and coordination chemistry, highlighting the technique’s growing impact and potential for future studies.

M-edge XANES↗

SXP 214: an X-ray pulsar in the small magellanic cloud, crossing the circumstellar disk of the companion

Located in the Small Magellanic Cloud (SMC), SXP 214 is an X-ray pulsar in a high mass X-ray binary system with a Be-star companion. A recent survey of the SMC under a Chandra X-ray Visionary program found that the source was in a transition when the X-ray flux was on a steady rise. The Lomb–Scargle periodogram revealed a pulse period of 211.49 ± 0.42 s, which is significantly (>5σ) shorter than the previous measurements made with XMM-Newton and RXTE. This implies that the system has gone through sudden spin-up episodes recently. The pulse profile shows a sharp eclipse-like feature with a modulation amplitude of >95%. The linear rise of the observed X-ray luminosity from ≲2× to 7×10{sup 35} erg s{sup −1} is correlated with a steady softening of the X-ray spectrum, which can be described by the changes in the local absorption from N {sub H} ∼ 10{sup 24} to ≲10{sup 20} cm{sup −2} for an absorbed power-law model. The soft X-ray emission below 2 keV was absent in the early part of the observation when only the pulsating hard X-ray component was observed, whereas at later times, both soft and hard X-ray components were observed to be pulsating. A likely explanation is that the neutron star was initially hidden in the circumstellar disk of the companion, and later came out of the disk with the accreted material that continued fueling the observed pulsation.

79 ASTRONOMY AND ASTROPHYSICS↗

Spectrally resolved localized states in GaAs 1– x Bi x

In this study, the role of localized states and their influence on the broader band structure remains a crucial question in understanding the band structure evolution in GaAs 1-x Bi x . Here in this work, we present clear spectroscopic observations of recombination at several localized states in GaAs 1-x Bi x . Sharp and recognizable photoluminescence features appear in multiple samples and redshift as a function of GaBi fraction between x = 0.16% and 0.4% at a linearized rate of 34 meV per % Bi, weaker than the redshift associated with band-to-band recombination. Interpreting these results in terms of radiative recombination between localized holes and free electrons sheds light on the relative movement of the conduction band minimum and the characteristics of localized bismuth-related trap states in GaAs 1-x Bi x alloys.

36 MATERIALS SCIENCE↗