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Redox-Induced Structural Reorganization Dictates Kinetics of Cobalt(III) Hydride Formation via Proton-Coupled Electron Transfer
Two-electron, one-proton reactions of a family of [CoCp(dxpe)(NCCH 3 )] 2+ complexes (Cp = cyclopentadienyl, dxpe = 1,2-bis(di(aryl/alkyl)phosphino)ethane) form the corresponding hydride species [HCoCp(dxpe)] + through a stepwise proton-coupled electron transfer process. For three [CoCp(dxpe)(NCCH 3 )] 2+ complexes (dxpe = dppe (1,2-bis(diphenylphosphino)ethane), depe (1,2-bis(diethylphosphino)ethane), and dcpe (1,2-bis(dicyclohexylphosphino)ethane)), peak shift analysis was employed to quantify apparent proton transfer rate constants from cyclic voltammograms recorded with acids ranging 22 pK a units. The apparent proton transfer rate constants correlate with the strength of the proton source for weak acids, but these apparent proton transfer rate constants curiously plateau (k pl ) as the reaction becomes increasingly exergonic. The absolute apparent proton transfer rate constants across both these regions correlate with the steric bulk of the chelating diphosphine ligand, with bulkier ligands leading to slower kinetics (k plateau,depe = 3.5 x 10 7 M -1 s -1 , k plateau,dppe = 1.7 x 10 7 M -1 s -1 , k plateau,dcpe = 7.1 x 10 4 M -1 s -1 ). Mechanistic studies were conducted to identify the cause of the aberrant $k_PT^{app}$–ΔpK a trends. When the deuterated acids are employed, deuterium incorporation in the Cp ring is observed, indicating protonation of the CoCp(dxpe) species to form the corresponding hydride proceeds via initial ligand protonation. Digital simulations of cyclic voltammograms show ligand loss accompanying initial reduction gates subsequent PCET activity at higher driving forces. Together, these experiments reveal the details of the reaction mechanism: reduction of the Co(III) species is followed by dissociation of the bound acetonitrile ligand, subsequent reduction of the unligated Co(II) species to form a Co(I) species is followed by protonation, which occurs at the Cp ring, followed by tautomerization to generate the stable Co(III)-hydride product [HCoCp(dxpe)] + . Analysis as a function of chelating disphosphine ligand, solvent, and acid strength reveals that the ligand dissociation equilibrium is directly influenced by the steric bulk of the phosphine ligands and gates protonation, giving rise to the plateau of apparent proton transfer rate constant with strong acids. The complexity of the reaction mechanism underpinning hydride formation, encompassing dynamic behavior of the entire ligand set, highlights the critical need to understand elementary reaction steps in proton-coupled electron transfer reactions.
Monomeric prefusion structure of an extremophile gamete fusogen and stepwise formation of the postfu
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The mesoscale order of nacreous pearls
A pearl’s distinguished beauty and toughness are attributable to the periodic stacking of aragonite tablets known as nacre. Nacre has naturally occurring mesoscale periodicity that remarkably arises in the absence of discrete translational symmetry. Gleaning the inspiring biomineral design of a pearl requires quantifying its structural coherence and understanding the stochastic processes that influence formation. By characterizing the entire structure of pearls (~3 mm) in a cross-section at high resolution, we show that nacre has medium-range mesoscale periodicity. Self-correcting growth mechanisms actively remedy disorder and topological defects of the tablets and act as a countervailing process to long-range disorder. Nacre has a correlation length of roughly 16 tablets (~5.5 µm) despite persistent fluctuations and topological defects. For longer distances (>25 tablets ~8.5 µm), the frequency spectrum of nacre tablets follows f –1.5 behavior, suggesting that growth is coupled to external stochastic processes—a universality found across disparate natural phenomena, which now includes pearls.
What is Important? Morphological Asymmetries are Useful Predictors of Star Formation Rates of Star-forming Galaxies in SDSS Stripe 82
The morphology and structure of galaxies reflect their star formation and assembly histories. We use the framework of mutual information (MI) to quantify the interdependence among several structural variables and to rank them according to their relevance for predicting the specific star formation rate (SSFR) by comparing the MI of the predictor variables with the SSFR and penalizing variables that are redundant. We apply this framework to study ~3700 face-on star-forming galaxies (SFGs) with varying degrees of bulge dominance and central concentration and with stellar mass $M$ * ≈ 10 9 $M$ ⊙ at redshift $z$ = 0.02–0.12. We use the Sloan Digital Sky Survey (SDSS) Stripe 82 deep $i$-band imaging data, which improve measurements of asymmetry and bulge dominance indicators. We find that star-forming galaxies are a multiparameter family. In addition to $M$ * , asymmetry emerges as the most powerful predictor of SSFR residuals of SFGs, followed by bulge prominence/concentration. Star-forming galaxies with higher asymmetry and stronger bulges have higher SSFR at a given $M$ * . In conclusion, the asymmetry reflects both irregular spiral arms and lopsidedness in seemingly isolated SFGs and structural perturbations by galaxy interactions or mergers.
MHD simulations of cold bubble formation from 2/1 tearing mode during massive gas injection in a tokamak
Massive gas injection (MGI) experiments have been carried out in many tokamaks to study disruption dynamics and mitigation schemes. Two events often observed in those experiments are the excitation of the m = 2, n = 1 magnetohydrodynamic mode, and the formation of cold bubble structure in the temperature distribution before the thermal quench (TQ). Here m is the poloidal mode number, n the toroidal mode number. The physics mechanisms underlying those phenomena, however, have not been entirely clear. In this work, our recent NIMROD simulations of the MGI process in a tokamak have reproduced the main features of both events, which has allowed us to examine and establish the causal relation between them. In these simulations, the 3/1 and 2/1 islands are found to form successively after the arrival of impurity ion cold front at the corresponding q = 3 and q = 2 rational surfaces. At the interface between impurity and plasma, a local thin current sheet forms due to an enhanced local pressure gradient and moves inward following the gas cold front, this may contribute to the formation of a dominant 2/1 mode. Following the growth of the 2/1 tearing mode, the impurity penetration into the core region inside the q = 2 surface gives rise to the formation of the cold bubble temperature structure and initiates the final TQ. Here, a subdominant 1/1 mode developed earlier near the q = 1 surface alone does not cause such a cold bubble formation, however, the exact manner of the preceding impurity penetration depends on the nature of the 1/1 mode: kink-tearing or quasi-interchange.
In Situ Transmission Electron Microscopy Study of Conductive Filament Formation in Copper Oxides
The structural and electrical property changes of two types of copper oxides (CuO and Cu 2 O) under voltage bias are studied with in situ transmission electron microscopy (TEM). The phases of different materials are confirmed with electron diffraction. In both types of oxides, dynamic conductive path formation and dissolution are observed. The decrease in resistance of CuO film is found to be accompanied with the formation of Cu 4 O 3 phase where the electric field strength is highest. We also find that the decrease in resistivity of Cu 2 O film is more extensive and occurs in an area depending on the level of current compliance. In conclusion, the physical mechanisms responsible for the observations and their implications for the formation of conducting regions in copper oxide-based memristors are discussed.
Influence of AA6061 surface preparation on the resistance to surface degradation of thermally grown boehmite films
Understanding substrate–coating interactions is crucial for designing durable, corrosion-resistant systems. This study investigates the effects of surface treatments— polishing, acid etching, and alkaline etching—on AA6061 aluminum alloy and its thermally grown boehmite coatings. Surface treatments were found to significantly alter boehmite film properties by modifying the alloy’s surface composition. X-ray photoelectron spectroscopy revealed a 10% alumina drop after acid etching alongside chemisorbed species formation in wet treatments. Structural analysis, including grazing incidence X-ray diffraction and TEM, showed α-Al 2 O 3 formation on polished surfaces, improving wear resistance but inducing cathodic E corr shifts, pointing to higher corrosion susceptibility. In contrast, acid and alkaline etching produced anodic E corr shifts with stable, pit-free films observed via potentiodynamic scans. Electrochemical impedance spectroscopy highlighted reduced oxide resistance with extended boehmite growth. The findings emphasize the role of surface pre-treatments and boehmite optimization in balancing durability and corrosion resistance for AA6061 substrates.
What Determines the fcc-bcc Structural Transformation in Shock Compressed Noble Metals?
Abstract not provided
Seasonal/Spatial Vertical New Particle Formation Variation Study (SSVNV) Field Campaign Report
The Seasonal/Spatial Vertical NPF Variation Study (SSVNV) campaign was conducted to investigate vertically resolved aerosol variability, boundary-layer structure, and new particle formation (NPF) processes across contrasting atmospheric environments through coordinated tethered balloon system (TBS) observations during U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) User Facility fixed-site measurements (Dexheimer et al. 2026). The campaign leveraged the overlapping deployments of the third ARM Mobile Facility (AMF3) at Bankhead National Forest (BNF; Kuang et al. 2023, 2026), Alabama, and the first ARM Mobile Facility 1 (AMF1) Coast-Urban-Rural Gradient Atmospheric Experiment (CoURAGE) in the Baltimore region. The campaign was operated by the TBS team led by Darielle Dexheimer from Sandia National Laboratories, in collaboration with the BNF site science team lead by Chongai Kuang from Brookhaven National Laboratory and the ARM team.
Modeling Molecular Hydrogen in Low-metallicity Galaxies
We use a suite of hydrodynamics simulations of the interstellar medium (ISM) within a galactic disk, which includes radiative transfer, a nonequilibrium model of molecular hydrogen, and a realistic model for star formation and feedback, to study the structure of the ISM and H 2 abundance as a function of local ISM properties. We show that the star formation rate and structure of the ISM are sensitive to the metallicity of the gas with a progressively smoother density distribution with decreasing metallicity. In addition to the well-known trend of the H I–H 2 transition shifting to higher densities with decreasing metallicity, the maximum achieved molecular fraction in the ISM drops drastically at Z ≲ 0.2 Z ⊙ as the formation time of H 2 becomes much longer than a typical lifetime of dense regions of the ISM. We present accurate fitting formulae for both volumetric and projected ƒ H 2 measured on different scales as a function of gas metallicity, UV radiation field, and gas density. We show that when the formulae are applied to the patches in the simulated galaxy, the overall molecular gas mass is reproduced to better than a factor of ≲1.5 across the entire range of metallicities and scales. We also show that the presented fit is considerably more accurate than any of the previous ƒ H 2 models and fitting formulae in the low-metallicity regime. The fit can thus be used for modeling molecular gas in low-resolution simulations and semi-analytic models of galaxy formation in the dwarf and high-redshift regimes.
High-pressure response of vibrational properties of b-As x P 1– x : in situ Raman studies
The structural evolution of black arsenic-phosphorous (b-As x P 1–x ) alloys with varying arsenic concentrations was investigated under hydrostatic pressure using in situ Raman spectroscopy. High-pressure experiments were conducted using a diamond anvil cell, which revealed pressure-induced shifts in vibrational modes associated with P–P bonds (A 1 g , A 2 g , ${B}_{2g}$), As–As bonds (A 1 g , A 2 g , ${{B}}_{2g}$), and As–P bonds in b-As x P 1–x alloys. Two distinct pressure regimes were observed. In the first regime (region I), all vibrational modes exhibited a monotonic upshift, indicating phonon hardening due to hydrostatic pressure. In the second regime (region II), As 0.4 P 0.6 and As 0.6 P 0.4 alloys displayed a linear blueshift (or negligible change in some modes) at a reduced rate, suggesting local structural reorganization with less compression on the bonds. Notably, the alloy with the highest As concentration, As 0.8 P 0.2 , exhibited anomalous behavior in the second pressure regime, with a downward shift observed in all As–As and As–P Raman modes (and some P–P modes). Interestingly, the emergence of new peaks corresponding to the E g mode and A 1g mode of the gray-As phase was observed in this pressure range, indicating compressive strain-induced structural changes. The anomalous change in region II confirms the formation of a new local structure, characterized by elongation of the P–P, As–As, and As–P bonds along the zigzag direction within the b-As x P 1–x phase, possibly near the grain boundary. Additionally, a gray-As phase undergoes compressive structural changes. This study underscores the significance of pressure in inducing structural transformations and exploring novel phases in two-dimensional materials, including b-As x P 1–x alloys.
Symmetry-mode analysis for local structure investigations using pair distribution function data
Symmetry-adapted distortion modes provide a natural way of describing distorted structures derived from higher-symmetry parent phases. Structural refinements using symmetry-mode amplitudes as fit variables have been used for at least ten years in Rietveld refinements of the average crystal structure from diffraction data; more recently, this approach has also been used for investigations of the local structure using real-space pair distribution function (PDF) data. Here, the value of performing symmetry-mode fits to PDF data is further demonstrated through the successful application of this method to two topical materials: TiSe2, where a subtle but long-range structural distortion driven by the formation of a charge-density wave is detected, and MnTe, where a large but highly localized structural distortion is characterized in terms of symmetry-lowering displacements of the Te atoms. Here, the analysis is performed using fully open-source code within the DiffPy framework via two packages developed for this work: isopydistort, which provides a scriptable interface to the ISODISTORT web application for group theoretical calculations, and isopytools, which converts the ISODISTORT output into a DiffPy-compatible format for subsequent fitting and analysis. These developments expand the potential impact of symmetry-adapted PDF analysis by enabling high-throughput analysis and removing the need for any commercial software.
TRACE Input Modernization
This work presents a Tom’s Obvious Minimal Language (TOML)-based representation of input for the US Nuclear Regulatory Commission’s TRAC/RELAP Advanced Computational Engine (TRACE) thermal hydraulics code. Implemented using the Workbench Analysis Sequence Processor (WASP), the approach maps traditional TRACE input structures to a hierarchical format composed of named parameters, typed values, and native data collections. The resulting representation preserves TRACE’s existing modeling capabilities while providing a modern, structured interface for model development and management. WASP further extends TOML through a file import directive that supports modular model composition and reusable input organization. In addition, WASP provides extended array data entry convenience with various data repeat and interpolation capabilities. Examples of the new TOML syntax are provided for major TRACE input categories, including hydraulic components, heat structures, control systems, and trip logic. The TOML representation establishes a foundation for improved validation, tooling, automation, and model maintainability while remaining compatible with existing TRACE workflows. To facilitate migration to the TOML-based input format, the TRACE executable now supports conversion of native TRACE input into an intermediate JSON representation. A Python utility subsequently transforms the JSON data into an equivalent TOML model. Lastly, the TRACE executable now supports execution using TOML-formatted input.
Defect chemistry of Cr-B binary and Cr-Al-B MAB phases: Effects of covalently bonded B networks
Transition metal borides, which are three-dimensional (3D) layered materials containing covalently bonded B networks, have shown a number of excellent properties, such as radiation resistance and the ability to act as a diffusion barrier in integrated circuits. However, defect behavior, which controls many of the materials’ properties, has remained unknown in these materials. In this work, we investigate the effects of the B networks on the defect chemistry in both binary borides (CrB, Cr 3 B 4 , Cr 2 B 3 ) and ternary MAB phases (Cr 2 AlB 2 , Cr 3 AlB 4 , Cr 4 AlB 6 ) using first-principles calculations. We find that increasing the number of B rings in the structure leads to lower formation energies and higher concentrations of Frenkel pairs. The results can be explained by the fact that the strongest Cr-B bond is weakened when borides have more B rings, leading to a reduction in the formation energy of Cr and B vacancies. Also, the bonds associated with Cr atoms bonded within B rings are softer in structures containing more B rings, which allows Cr interstitials to form with a lower energy cost and contributes to an increase in the concentration of Cr interstitials.
Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes
Multivalent counterion-induced bridging interactions have been identified as the key mechanism of drastic collapse of the height of polyelectrolyte (PE) brushes. In this article, we employ all-atom molecular dynamics (MD) simulations to quantify the bridging interactions in PE brushes for counterions of different sizes and valences. We identify that unlike the current notion, bridging interactions are not the sole function of the counterion valence. Rather the bridging interactions depend on the fraction of counterions (of a given type) that get physically condensed on the PE backbone as well as the size of the counterion solvation shell. These mechanisms ensure that certain monovalent counterions demonstrate much stronger bridging interactions than that witnessed for certain divalent and trivalent counterions, while certain counterions of identical valences show drastically different bridging. Here, we argue that these counterion-specific bridging interactions eventually enable not only the significant reduction of the PE brush height in presence of certain multivalent screening counterions, but may also give rise to scenarios where the brush height reduction for certain monovalent counterions is larger than certain divalent and trivalent counterions. This latter observation contradicts the experimental findings where the multivalent counterions invariably led to a larger decrease in the height of the PE brushes: we argue that this discrepancy stems from the fact that in our simulations we only consider densely grafted and short (and hence less flexible) PE brushes that hinder the formation of different laterally inhomogeneous structures (like pinned micelles and cylindrical bundles) that would have led to a larger brush height reduction (in experiments, which invariably consider longer and less densely grafted brushes, the formation of such inhomogeneous structures are primarily responsible for larger brush height reduction in presence of multivalent counterions). Finally, we also probe the dynamic properties of the counterions (i.e., their time-dependent displacements) and their bridging interactions (i.e., lifetime of bridging interactions).
Orientational Pair Correlations and Local Structure of Benzonitrile from Molecular Dynamics Simulations with Comparisons to Experiments [plus supplemental information]
Here, we present an experimentally parametrized molecular dynamics study of single-molecule and collective orientational relaxation in neat benzonitrile through the analysis of the reorientational anisotropy and polarizability anisotropy time-correlation function (PA-TCF). The simulations show that the PA-TCF is dominated by collective reorientation after 20 ps. Collective reorientation is found to be slower than single-molecule reorientation by a factor of 1.67, consistent with recent experiments. The simulations provide direct evidence of local antiparallel benzonitrile configurations. These structures, which have been the center of some debate, are responsible for the slower rate of collective vs. single-molecule reorientation in the liquid. Further structural analysis indicates that significant Coulombic interactions between the nitrile group and hydrogen atoms on adjacent molecules play a role in the formation of the antiparallel structures. The single-molecule dynamics reflected in the anisotropy are complex and consist of a ballistic regime, restricted angular diffusion, and spatially anisotropic free diffusion. The principal components of the rotational diffusion tensor are independently obtained and shown to reproduce the free diffusion regime of the anisotropy for each principal axis according to the predictions of a previous theory.
Rational Design of Novel Biomimetic Sequence-Defined Polymers for Mineralization Applications
Silica biomineralization is a naturally occurring process, wherein organisms use proteins and other biological structures to direct the formation of complex, hierarchical nanostructures. Discovery and characterization of such proteins and their underlying mechanisms spurred significant efforts to identify routes for biomimetic mineralization that reproduce the exquisite shapes and size selectivities found in nature. A common strategy has been the use of short peptide sequences with chemistry mimicking those found in natural systems, such as the use of the silaffin-derived R5 peptide. While progress has been made using this approach, there are many limitations that have prevented breakthroughs in biomimicry. To advance our ability to use charged macromolecules for silica formation, we propose to use sequence-defined synthetic polymers known as peptoids, or N-substituted polyglycines, which present significant capability for the precise tuning of sequence and structure beyond what can often be achieved with peptides alone. This study presents a computationally predicted design of these polymers that leads to the controlled formation of silica nanomaterials. We investigate surface adsorption and the mineralization process through analysis of binding mechanisms and energetics of the R5 system. Next, we synthesized two R5-inspired peptoids and validated our prediction in the design of mineralization polymers through characterization using surface plasmon resonance and electron microscopy. Here, this computationally guided study holds great promise for designing new sequences with unprecedented control of the placement of chemical functional groups, thus allowing for further unraveling of silicification mechanisms and the eventual design of sequence-defined synthetic polymers leading to the predictive synthesis of nanostructured functional materials.