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At least 703 records · Page 39

3D pattern formation of a protein–membrane suspension

Many essential cellular processes, including cell division and the establishment of cell polarity during embryogenesis, are regulated by pattern-forming proteins. These proteins often need to bind to a substrate, such as the cell membrane, onto which they interact and form two-dimensional (2D) patterns. It is unclear how the membrane’s continuity and dimensionality impact pattern formation. Here, we address this gap using the MinDE system, a prototypical example of pattern-forming membrane proteins. We show that when the lipid substrate is fragmented into submicrometer-sized diffusive liposomes, adenosine triphosphate-driven protein–protein interactions generate three-dimensional (3D) spatially extended patterns, despite the complete loss of membrane continuity. Remarkably, these 3D patterns emerge at scales four orders of magnitude larger than the individual liposomes. By systematically varying protein concentration, liposome size, and density, we observed and characterized a variety of 3D dynamical patterns not seen on continuous 2D membranes, including traveling waves, dynamical spirals, and a coexistence phase. Simulations and linear stability analysis of a coarse-grained model revealed that the physical properties of the dispersed membrane effectively rescale both the protein–membrane binding rates and diffusion, two key parameters governing pattern formation and wavelength selection. These findings highlight the robustness of Min’s pattern-forming ability, suggesting that protein–membrane suspensions could serve as an adaptable template for studying out-of-equilibrium self-organization in 3D, beyond in vivo contexts.

36 MATERIALS SCIENCE↗

Application of Fourier analysis to multispectral/spatial recognition

One approach for investigating spectral response from materials is to consider spatial features of the response. This might be accomplished by considering the Fourier spectrum of the spatial response. The Fourier Transform may be used in a one-dimensional to multidimensional analysis of more than one channel of data. The two-dimensional transform represents the Fraunhofer diffraction pattern of the image in optics and has certain invariant features. Physically the diffraction pattern contains spatial features which are possibly unique to a given configuration or classification type. Different sampling strategies may be used to either enhance geometrical differences or extract additional features.

Hornung, R. J.↗

High-latitude distributions of plasma waves and spatial irregularities from DE 2 alternating current electric field observations

The high-latitude spatial distributions of average signal intensities in 12 frequency channels between 4 Hz and 512 kHz as measured by the ac electric field spectrometers on the DE-2 spacecraft are analyzed for 18 mo of measurements. In MLT-INL (magnetic local time-invariant latitude) there are three distinct distributions that can be identified with 4-512 Hz signals from spatial irregularities and Alfven waves, 256-Hz to 4.1-kHz signals from ELF hiss, and 4.1-64 kHz signals from VLF auroral hiss, respectively. Overlap between ELF hiss and spatial irregularity signals occurs in the 256-512 Hz band. VLF hiss signals extend downward in frequency into the 1.0-4.1 kHz band and upward into the frequency range 128-512 kHz. The distinctly different spatial distribution patterns for the three bands, 4-256 Hz, 512-1204 Hz, and 4.1-64 kHz, indicate a lack of any causal relationships between VLF hiss, ELF hiss, and lower-frequency signals from spatial irregularities and Alfven waves.

Heppner, J. P.↗

The Analysis of the Patterns of Radiation-Induced DNA Damage Foci by a Stochastic Monte Carlo Model of DNA Double Strand Breaks Induction by Heavy Ions and Image Segmentation Software

To create a generalized mechanistic model of DNA damage in human cells that will generate analytical and image data corresponding to experimentally observed DNA damage foci and will help to improve the experimental foci yields by simulating spatial foci patterns and resolving problems with quantitative image analysis. Material and Methods: The analysis of patterns of RIFs (radiation-induced foci) produced by low- and high-LET (linear energy transfer) radiation was conducted by using a Monte Carlo model that combines the heavy ion track structure with characteristics of the human genome on the level of chromosomes. The foci patterns were also simulated in the maximum projection plane for flat nuclei. Some data analysis was done with the help of image segmentation software that identifies individual classes of RIFs and colocolized RIFs, which is of importance to some experimental assays that assign DNA damage a dual phosphorescent signal. Results: The model predicts the spatial and genomic distributions of DNA DSBs (double strand breaks) and associated RIFs in a human cell nucleus for a particular dose of either low- or high-LET radiation. We used the model to do analyses for different irradiation scenarios. In the beam-parallel-to-the-disk-of-a-flattened-nucleus scenario we found that the foci appeared to be merged due to their high density, while, in the perpendicular-beam scenario, the foci appeared as one bright spot per hit. The statistics and spatial distribution of regions of densely arranged foci, termed DNA foci chains, were predicted numerically using this model. Another analysis was done to evaluate the number of ion hits per nucleus, which were visible from streaks of closely located foci. In another analysis, our image segmentaiton software determined foci yields directly from images with single-class or colocolized foci. Conclusions: We showed that DSB clustering needs to be taken into account to determine the true DNA damage foci yield, which helps to determine the DSB yield. Using the model analysis, a researcher can refine the DSB yield per nucleus per particle. We showed that purely geometric artifacts, present in the experimental images, can be analytically resolved with the model, and that the quantization of track hits and DSB yields can be provided to the experimentalists who use enumeration of radiation-induced foci in immunofluorescence experiments using proteins that detect DNA damage. An automated image segmentaiton software can prove useful in a faster and more precise object counting for colocolized foci images.

Ponomarev, Artem↗

Sensitivity of meteorological-forcing resolution on hydrologic variables

Projecting the spatiotemporal changes in water resources under a no-analog future climate requires physically based integrated hydrologic models which simulate the transfer of water and energy across the earth's surface. These models show promise in the context of unprecedented climate extremes given their reliance on the underlying physics of the system as opposed to empirical relationships. However, these techniques are plagued by several sources of uncertainty, including the inaccuracy of input datasets such as meteorological forcing. These datasets, usually derived from climate models or satellite-based products, are typically only resolved on the order of tens to hundreds of kilometers, while hydrologic variables of interest (e.g., discharge and groundwater levels) require a resolution at much smaller scales. In this work, a high-resolution hydrologic model is forced with various resolutions of meteorological forcing (0.5 to 40.5 km) generated by a dynamical downscaling analysis from the regional climate model Weather Research and Forecasting (WRF). The Cosumnes watershed, which spans the Sierra Nevada and Central Valley interface of California (USA), exhibits semi-natural flow conditions due to its rare undammed river basin and is used here as a test bed to illustrate potential impacts of various resolutions of meteorological forcing on snow accumulation and snowmelt, surface runoff, infiltration, evapotranspiration, and groundwater levels. Results show that the errors in spatial distribution patterns impact land surface processes and can be delayed in time. Localized biases in groundwater levels can be as large as 5–10 m and 3 m in surface water. Most hydrologic variables reveal that biases are seasonally and spatially dependent, which can have serious implications for model calibration and ultimately water management decisions.

54 ENVIRONMENTAL SCIENCES↗

Radio Morphology of Red Geysers

We present 150 MHz, 1.4 GHz, and 3 GHz radio imaging (LoTSS, FIRST, and VLASS) and spatially resolved ionized gas characteristics (SDSS IV-MaNGA) for 140 local ($z$ < 0.1) early-type red geyser galaxies. These galaxies have a low star formation activity (with a star formation rate, SFR, ~ 0.01 $M$ ⊙ yr -1 ) but show unique extended patterns in spatially resolved emission-line maps that have been interpreted as large-scale ionized winds driven by active galactic nuclei (AGN). In this work, we confirm that red geysers host low-luminosity radio sources ($L$ 1.4GHz ~ 10 22 $WHz$ -1 ). Out of 42 radio-detected red geysers, 32 are spatially resolved in LoTSS and FIRST, with radio sizes varying between ~5–25 kpc. Three sources have radio sizes exceeding 40 kpc. A majority display a compact radio morphology and are consistent with either low-power compact radio sources (FR0 galaxies) or radio-quiet quasars. They may be powered by small-scale AGN-driven jets that remain unresolved at the current 5'' resolution of radio data. The extended radio sources, not belonging to the "compact" morphological class, exhibit steeper spectra with a median spectral index of -0.67, indicating the dominance of lobed components. Furthermore, the red geysers hosting extended radio sources also have the lowest specific SFRs, suggesting they either have a greater impact on the surrounding interstellar medium or are found in more massive halos on average. The degree of alignment of the ionized wind cone and the extended radio features are either 0° or 90°, indicating possible interaction between the interstellar medium and the central radio AGN.

79 ASTRONOMY AND ASTROPHYSICS↗

Comparison of Radiative Energy Flows in Observational Datasets and Climate Modeling

This study examines radiative flux distributions and local spread of values from three major observational datasets (CERES, ISCCP, and SRB) and compares them with results from climate modeling (CMIP3). Examinations of the spread and differences also differentiate among contributions from cloudy and clear-sky conditions. The spread among observational datasets is in large part caused by noncloud ancillary data. Average differences of at least 10Wm(exp -2) each for clear-sky downward solar, upward solar, and upward infrared fluxes at the surface demonstrate via spatial difference patterns major differences in assumptions for atmospheric aerosol, solar surface albedo and surface temperature, and/or emittance in observational datasets. At the top of the atmosphere (TOA), observational datasets are less influenced by the ancillary data errors than at the surface. Comparisons of spatial radiative flux distributions at the TOA between observations and climate modeling indicate large deficiencies in the strength and distribution of model-simulated cloud radiative effects. Differences are largest for lower-altitude clouds over low-latitude oceans. Global modeling simulates stronger cloud radiative effects (CRE) by +30Wmexp -2) over trade wind cumulus regions, yet smaller CRE by about -30Wm(exp -2) over (smaller in area) stratocumulus regions. At the surface, climate modeling simulates on average about 15Wm(exp -2) smaller radiative net flux imbalances, as if climate modeling underestimates latent heat release (and precipitation). Relative to observational datasets, simulated surface net fluxes are particularly lower over oceanic trade wind regions (where global modeling tends to overestimate the radiative impact of clouds). Still, with the uncertainty in noncloud ancillary data, observational data do not establish a reliable reference.

Raschke, Ehrhard↗

Space and time aliasing structure is monthly mean polar-orbiting satellite data

Monthly mean wind fields from the European Remote Sensing Satellite (ERS1) scatterometer are presented. A banded structure which resembles the satellite subtrack is clearly and consistently apparent in the isotachs as well as the u and v components of the routinely produced fields. The structure also appears in the means of data from other polar-orbiting satellites and instruments. An experiment is designed to trace the cause of the banded structure. The European Centre for Medium-Range Weather Forecast (ECMWF) gridded surface wind analyses are used as a control set. These analyses are also sampled with the ERS1 temporal-spatial samplig pattern to form a simulated scatterometer wind set. Both sets are used to create monthly averages. The banded structures appear in the monthly mean simulated data but do not appear in the control set. It is concluded that the source of the banded structure lies in the spatial and temporal sampling of the polar-orbiting satellite which results in undersampling. The problem involves multiple timescales and space scales, oversampling and under-sampling in space, aliasing in the time and space domains, and preferentially sampled variability. It is shown that commonly used spatial smoothers (or filters), while producing visually pleasing results, also significantly bias the true mean. A three-dimensional spatial-temporal interpolator is designed and used to determine the mean field. It is found to produce satisfactory monthly means from both simulated and real ERS1 data. The implications to climate studies involving polar-orbiting satellite data are discussed.

Zeng, Lixin↗

A space-time stochastic model of rainfall for satellite remote-sensing studies

A model of the spatial and temporal distribution of rainfall is described that produces random spatial rainfall patterns with these characteristics: (1) the model is defined on a grid with each grid point representing the average rain rate over the surrounding grid box, (2) rain occurs at any one grid point, on average, a specified percentage of the time and has a lognormal probability distribution, (3) spatial correlation of the rainfall can be arbitrarily prescribed, and (4) time stepping is carried out so that large-scale features persist longer than small-scale features. Rain is generated in the model from the portion of a correlated Gaussian random field that exceeds a threshold. The portion of the field above the threshold is rescaled to have a lognormal probability distribution. Sample output of the model designed to mimic radar observations of rainfall during the Global Atmospheric Research Program Atlantic Tropical Experiment (GATE), is shown. The model is intended for use in evaluating sampling strategies for satellite remote-sensing of rainfall and for development of algorithms for converting radiant intensity received by an instrument from its field of view into rainfall amount.

Bell, Thomas L.↗

Modeling Electric Vehicle Charging Load Using Origin-Destination Data

The accelerating adoption of electric vehicles (EVs) poses challenges to the power grid, necessitating precise representation of mobility patterns for effective infrastructure upgrades. Traditional simulation-based charging demand estimation faces limitations in generating trip chains reflective of actual travel patterns without complex network modeling. Hence, an innovative agent-based trip chain generation model is introduced to overcome these challenges. Drawing from the National Household Travel Survey (NHTS) and the NextGen NHTS origin-destination add-on data for Clarke County, Georgia, this study proposes a simulation method capturing both temporal and spatial mobility patterns without relying on extensive network topology data. The resulting trip chains predict EV charging load at the Census Block Group level, validated with a 1.03 correlation to actual trip counts, affirming their reflective accuracy. Two charging scenarios, residential-only and charging-everywhere, reveal distinct demand profiles. The charging-everywhere scenario aligns closely with the trip profile, while the residential-only scenario exhibits an afternoon peak slightly surpassing the former. This study contributes a data-driven charging demand estimation methodology, offering critical insights for grid resiliency planning amid the evolving landscape of EV adoption.

Pan, Melrose↗

Alaska Transportation & Infrastructure - Identifying Permafrost Subsidence Using NASA Earth Observations to Pinpoint Road & Infrastructure Vulnerability in Fairbanks, Alaska

A rapidly warming Arctic has compromised the structural integrity of critical infrastructure through accelerated permafrost thaw and thermokarst development underlying these areas. Infrastructure, including roads, bridges, and airports across the state of Alaska are particularly at risk, as permafrost underlies ~85% of the state. However, monitoring the impacts of permafrost thaw on infrastructure is largely limited to in situ observations and frequently identified after the damage is evident. In order to assist transportation and infrastructure decision-makers in Alaska, this project identified and quantified areas of surface subsidence near critical infrastructure. Seasonal interferograms were created using Sentinel-1 C-band Synthetic Aperture Radar (SAR) and L-band Uninhabited Aerial Vehicle SAR (UAVSAR) data to identify areas experiencing surface deformation. Additionally, Light Detection and Ranging (LiDAR) datasets were used to validate select interferograms created between 2017 and 2019. Validation of subsidence detection across platforms was performed over a 7x8 sq. kilometer field site for 2017. UAVSAR and Sentinel-1 seasonal deformation returns produced consistent spatial deformation patterns with residual root mean squared errors of 13 and 21 millimeters, respectively. These results suggest that both UAVSAR and Sentinel-1 platforms are capable of detecting surface subsidence. The higher resolution of UAVSAR is better able to resolve localized subsidence features of less than 80 meters, but is limited by temporal resolution.In conjunction, UAVSAR and Sentinel-1 can provide complementary spatial and temporal resolutions for subsidence analysis in the absence of in situ data.

Patrick Saylor↗

An Integrated Framework for Memory-Centric Analysis: From Trace Collection to Co-Design

The memory wall phenomenon—where advances in processor performance significantly outpace those in memory subsystems—poses a fundamental challenge for contemporary computing systems. In memory-bound applications, memory subsystem behavior dominates performance, yet existing analysis approaches present significant limitations: detailed microarchitectural simulators require days to weeks to simulate modest workloads; hardware performance counters provide only aggregate statistics that obscure temporal and spatial access patterns; and scaled simulation approaches face challenges in capturing certain behaviors that emerge at larger scales. These limitations reflect a processor-centric design philosophy increasingly misaligned with memory-bound workloads where detailed understanding of memory access patterns, cache hierarchy interactions, and contention is critical for effective optimization. This paper presents an integrated framework for memory-centric analysis that enables effective hardware-software co-design. We describe practical trace collection techniques, including hardware-assisted processor tracing with minimal overhead and portable software-based instrumentation with statistical sampling. We present multi-perspective analysis methods that examine memory behavior from temporal, sequential, spatial, and relational viewpoints, revealing distinct optimization opportunities invisible in aggregate metrics. We detail an architectural modeling framework that uses sampled traces with temporal interpolation and confidence-based filtering to evaluate cache and memory configurations. Evaluation on representative benchmarks demonstrates that this framework achieves practical accuracy (L2 cache errors of 2.64\%, confidence-filtered L3 errors of 9.92\%, bandwidth errors of 7.33\%) while providing substantial speedup (26.8×) over cycle-accurate simulation, enabling rapid design space exploration. We demonstrate how this integrated framework enables systematic identification of both hardware optimizations (memory controller tuning, bank partitioning, NUMA configuration) and software optimizations (data layout restructuring, prefetching strategies, memory-aware scheduling). Through this comprehensive treatment of the memory-centric analysis pipeline—from trace collection through architectural modeling to co-design application—we provide researchers and practitioners with practical techniques for addressing memory bottlenecks in contemporary computing systems.

Gajaria, Dhruv Mayur↗

Graph Theory Roots of Spatial Operators for Kinematics and Dynamics

Spatial operators have been used to analyze the dynamics of robotic multibody systems and to develop novel computational dynamics algorithms. Mass matrix factorization, inversion, diagonalization, and linearization are among several new insights obtained using such operators. While initially developed for serial rigid body manipulators, the spatial operators and the related mathematical analysis have been shown to extend very broadly including to tree and closed topology systems, to systems with flexible joints, links, etc. This work uses concepts from graph theory to explore the mathematical foundations of spatial operators. The goal is to study and characterize the properties of the spatial operators at an abstract level so that they can be applied to a broader range of dynamics problems. The rich mathematical properties of the kinematics and dynamics of robotic multibody systems has been an area of strong research interest for several decades. These properties are important to understand the inherent physical behavior of systems, for stability and control analysis, for the development of computational algorithms, and for model development of faithful models. Recurring patterns in spatial operators leads one to ask the more abstract question about the properties and characteristics of spatial operators that make them so broadly applicable. The idea is to step back from the specific application systems, and understand more deeply the generic requirements and properties of spatial operators, so that the insights and techniques are readily available across different kinematics and dynamics problems. In this work, techniques from graph theory were used to explore the abstract basis for the spatial operators. The close relationship between the mathematical properties of adjacency matrices for graphs and those of spatial operators and their kernels were established. The connections hold across very basic requirements on the system topology, the nature of the component bodies, the indexing schemes, etc. The relationship of the underlying structure is intimately connected with efficient, recursive computational algorithms. The results provide the foundational groundwork for a much broader look at the key problems in kinematics and dynamics. The properties of general graphs and trees of nodes and edge were examined, as well as the properties of adjacency matrices that are used to describe graph connectivity. The nilpotency property of such matrices for directed trees was reviewed, and the adjacency matrices were generalized to the notion of block weighted adjacency matrices that support block matrix elements. This leads us to the development of the notion of Spatial Kernel Operator SKO kernels. These kernels provide the basis for the development of SKO resolvent operators.

Jain, Abhinandan↗

Legacy surface change analyses of the 1993 Rock Valley earthquake sequence for direct comparison to planned NA-22 underground conventional high-explosive experiments (Source Physics Experiment 3 (SPE3) - RV/DC Task 1.3 FY22 Final Report)

Recent work under two previous phases of the NNSA NA-22 Source Physics Experiment (SPE) have shown that underground chemical high-explosive experiments can produce detectable surface changes that differ in spatial extent and vertical magnitude depending on the geologic media at the site (Schultz-Fellenz et al., 2018; 2020; Crawford et al., 2021). Neither of these two prior phases of SPE identified natural earthquake-related surface effects in the same region that occurred at a similar depth as the explosive experiments for direct comparison. While earthquakes can also produce surface changes that are detectable using remote sensing data analyses, it is expected that the pattern and spatial extent of surface changes would vary between earthquakes and explosions. However, no direct-observed surface-change signature comparison between earthquakes and explosions has ever been performed. The SPE Phase 3 Rock Valley/Direct Comparison (RV/DC) program presents a unique opportunity to investigate and characterize co-occurrence of both earthquakes and explosions. In this project, we worked to address five tasks in a workflow, as follows: 1. Identify and obtain existing high-resolution legacy satellite and aerial imagery as close in time before and after the 1993 Rock Valley earthquake sequence to temporally constrain the analyses. 2. Transform these pre-earthquake and post-earthquake datasets into digital elevation models (DEMs) using geospatial analysis software packages (e.g., ArcGIS, Agisoft Metashape, and Google Earth Engine). 3. Perform DEM differencing analyses to assess and quantify earthquake-related changes from the 1993 sequence, and develop map products that visualize these analyses. 4. Use the analyses from (3) to: (a) assess spatial distribution and magnitude of surface changes due to the 1993 Rock Valley earthquake sequence, and (b) determine parameters of forthcoming, planned explosion-related surface change data collection from sensors mounted on unmanned aerial vehicles (UAVs) (e.g., spatial extent of collection, design and density of survey control, sensors to deploy, forward speed and line spacing of UAV flight lines, flight altitude). 5. Develop a summary report on the analyses, including how the analyses define parameters and identify focus areas for any future surface change analytical field campaigns related to the explosive experiment. Analyzing these legacy data and identifying whether they can detect any surface changes related to the earthquake sequence facilitates opportunities for direct signature comparison of surface change from explosions at one location, which has never previously been performed. Comparing the surface change signatures from a co-located and depth-equivalent earthquake and an explosion could help to advance remote sensing event discrimination techniques. This report summarizes the work completed toward this ambitious goal.

42 ENGINEERING↗

Machine Learning Emulation of Spatial Deposition from a Multi-Physics Ensemble of Weather and Atmospheric Transport Models

In the event of an accidental or intentional hazardous material release in the atmosphere, researchers often run physics-based atmospheric transport and dispersion models to predict the extent and variation of the contaminant spread. These predictions are imperfect due to propagated uncertainty from atmospheric model physics (or parameterizations) and weather data initial conditions. Ensembles of simulations can be used to estimate uncertainty, but running large ensembles is often very time consuming and resource intensive, even using large supercomputers. In this paper, we present a machine-learning-based method which can be used to quickly emulate spatial deposition patterns from a multi-physics ensemble of dispersion simulations. We use a hybrid linear and logistic regression method that can predict deposition in more than 100,000 grid cells with as few as fifty training examples. Logistic regression provides probabilistic predictions of the presence or absence of hazardous materials, while linear regression predicts the quantity of hazardous materials. The coefficients of the linear regressions also open avenues of exploration regarding interpretability—the presented model can be used to find which physics schemes are most important over different spatial areas. A single regression prediction is on the order of 10,000 times faster than running a weather and dispersion simulation. However, considering the number of weather and dispersion simulations needed to train the regressions, the speed-up achieved when considering the whole ensemble is about 24 times. Ultimately, this work will allow atmospheric researchers to produce potential contamination scenarios with uncertainty estimates faster than previously possible, aiding public servants and first responders.

97 MATHEMATICS AND COMPUTING↗

Potential Impacts of Assimilating All-sky Satellite Infrared Radiances on Convection-Permitting Analysis and Prediction of Tropical Convection

Geostationary infrared satellite observations are spatially dense [< 1/(20 km)2] and temporally frequent (< 1/hour). These suggest the possibility of using these observations to constrain sub-synoptic features over data sparse regions, such as tropical oceans. In this study, the potential impacts of assimilating water vapor channel brightness temperature (WV-BT) observations from the geostationary Meteorological Satellite 7 (Meteosat-7) on tropical convection analysis and prediction were systematically examined through a series of ensemble data assimilation experiments. WV-BT observations were assimilated hourly into convection-permitting ensembles using Penn State’s ensemble square root filter (EnSRF). Comparisons against independently observed Meteosat-7 window channel brightness temperature (Window-BT) show that the assimilation of WV-BT generally improved the intensities and locations of large-scale cloud patterns at spatial scales larger than 100 km. However, comparisons against independent soundings indicate that the EnSRF analysis produced a much stronger dry bias than the no data assimilation experiment. This strong dry bias is associated with the use of the simulated WV-BT from the prior mean during the EnSRF analysis step. A stochastic variant of the ensemble Kalman filter (NoMeanSF) is proposed. The NoMeanSF algorithm was able to assimilate the WV-BT without causing such a strong dry bias and the quality of the analyses’ horizontal cloud pattern is similar to EnSRF’s analyses. Finally, deterministic forecasts initiated from the NoMeanSF analyses possess better horizontal cloud patterns above 500 km than those of the EnSRF. These results suggest that it might be better to assimilate all-sky WV-BT through the NoMeanSF algorithm than EnSRF algorithm.

Chan, Man-Yau↗

Elastic forces drive nonequilibrium pattern formation in a model of nanocrystal ion exchange

The widely used process of nanocrystal ion exchange operates out of thermodynamic equilibrium and can require mixing components of varying sizes. Here we use theory and computer simulation to study a simple model which captures these two basic features of ion exchange reactions. We show that a strong driving force for exchange among different-sized species creates nonequilibrium patterns within model nanocrystals. We further demonstrate that such patterns can be thermodynamically stable within core/shell nanocrystals. These results help us understand the heterostructures formed in ion-exchanged nanocrystals and suggest strategies for leveraging elasticity to design patterns in nanoscale materials. Chemical transformations, such as ion exchange, are commonly employed to modify nanocrystal compositions. Yet the mechanisms of these transformations, which often operate far from equilibrium and entail mixing diverse chemical species, remain poorly understood. Here we explore an idealized model for ion exchange in which a chemical potential drives compositional defects to accumulate at a crystal’s surface. These impurities subsequently diffuse inward. We find that the nature of interactions between sites in a compositionally impure crystal strongly impacts exchange trajectories. In particular, elastic deformations which accompany lattice-mismatched species promote spatially modulated patterns in the composition. These same patterns can be produced at equilibrium in core/shell nanocrystals, whose structure mimics transient motifs observed in nonequilibrium trajectories. Moreover, the core of such nanocrystals undergoes a phase transition—from modulated to unstructured—as the thickness or stiffness of the shell is decreased. Our results help explain the varied patterns observed in heterostructured nanocrystals produced by ion exchange and suggest principles for the rational design of compositionally patterned nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatial Heterogenous Redox Couples Degradation in Sodium-Ion Battery Cathode Materials and the Mitigation of Voltage Fade by Blocking Oxygen Release

The use of anionic redox has become a new paradigm for improving the energy density of rechargeable batteries, which is essential for improving the market competitiveness of sodium-ion batteries. However, issues such as voltage attenuation and cycling stability degradation persist in layered oxide anion redox cathode materials. Here, in this study, we systematically investigate the classic Na-ion cathode material Na 0.6 Li 0.2 Mn 0.8 O 2 , and the primary causes of voltage decay are identified as the activation of cations and the reduction in anion redox activity. In addition, the activation of cations is closely associated with anion reactions. Through the application of sophisticated multiscale synchrotron absorption spectroscopy and imaging techniques, we have identified a pronounced pattern of spatially dependent degradation in the evolution of redox couples, which is more evident from the material’s surface to its core. With this understanding, we introduced a surface fluorination approach that modulates the local chemical coordination environment. This strategy increases the formation energy of surface oxygen vacancies and locks transition metals oxide state. Consequently, it enables more reversible anionic redox reactions, which block the spatial progression of degradation and mitigates voltage decay.

25 ENERGY STORAGE↗