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At least 469 records · Page 26

Exciton and biexciton transient absorption spectra of CdSe quantum dots with varying diameters

Transient absorption (TA) spectroscopy of semiconductor nanocrystals (NCs) is often used for excited state population analysis, but recent results suggest that TA bleach signals associated with multiexcitons in NCs do not scale linearly with exciton multiplicity. In this manuscript, we probe the factors that determine the intensities and spectral positions of exciton and biexciton components in the TA spectra of CdSe quantum dots (QDs) of five diameters. We find that, in all cases, the peak intensity of the biexciton TA spectrum is less than 1.5 times that of the single exciton TA spectrum, in stark contrast to a commonly made assumption that this ratio is 2. The relative intensities of the biexciton and exciton TA signals at each wavelength are determined by at least two factors: the TA spectral intensity and the spectral offset between the two signals. We do not observe correlations between either of these factors and the particle diameter, but we find that both are strongly impacted by replacing the native organic surface-capping ligands with a hole-trapping ligand. These results suggest that surface trapping plays an important role in determining the absolute intensities of TA features for CdSe QDs and not just their decay kinetics. Our work highlights the role of spectral offsets and the importance of surface trapping in governing absolute TA intensities. It also conclusively demonstrates that the biexciton TA spectra of CdSe QDs at the band gap energy are less than twice as intense as those of the exciton.

Chemistry↗

Scenario development for safety assessment in deep geologic disposal of high-level radioactive waste and spent nuclear fuel: A review

Radiation and radioactive substances result in the production of radioactive wastes which require safe management and disposal to avoid risks to human health and the environment. To ensure permanent safe disposal, the performance of a deep geological repository for radioactive waste is assessed against internationally agreed risk-based standards. Assessing postclosure safety of the future system's evolution includes screening of features, events, and processes (FEPs) relevant to the situation, their subsequent development into scenarios, and finally the development and execution of safety assessment (SA) models. Global FEP catalogs describe important natural and man-made repository system features and identify events and processes that may affect these features into the future. By combining FEPs, many of which are uncertain, different possible future system evolution scenarios are derived. Repository licensing should consider both the reference or “base” evolution as well as alternative futures that may lead to radiation release, pollution, or exposures. Scenarios are used to derive and consider both base and alternative evolutions, often through production of scenario-specific SA models and the recombination of their results into an assessment of the risk of harm. Furthermore, while the FEP-based scenario development process outlined here has evolved somewhat since its development in the 1980s, the fundamental ideas remain unchanged. A spectrum of common approaches is given here (e.g., bottom–up vs. top–down scenario development, probabilistic vs. bounding handling of uncertainty), related to how individual numerical models for possible futures are converted into a determination as to whether the system is safe (i.e., how aleatoric uncertainty and scenarios are integrated through bounding or Monte Carlo approaches).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The structural basis of bacterial manganese import

Metal ions are essential for all forms of life. In prokaryotes, ATP-binding cassette (ABC) permeases serve as the primary import pathway for many micronutrients including the first-row transition metal manganese. However, the structural features of ionic metal transporting ABC permeases have remained undefined. Here, we present the crystal structure of the manganese transporter PsaBC from Streptococcus pneumoniae in an open-inward conformation. The type II transporter has a tightly closed transmembrane channel due to “extracellular gating” residues that prevent water permeation or ion reflux. Below these residues, the channel contains a hitherto unreported metal coordination site, which is essential for manganese translocation. Mutagenesis of the extracellular gate perturbs manganese uptake, while coordination site mutagenesis abolishes import. These structural features are highly conserved in metal-specific ABC transporters and are represented throughout the kingdoms of life. Collectively, our results define the structure of PsaBC and reveal the features required for divalent cation transport.

59 BASIC BIOLOGICAL SCIENCES↗

Neutron Imaging Using Grating Interferometry: Exploiting phase contrast and dark-field imaging for <1μm feature detection in bulk materials (Summary Report)

Radiography is an important non-destructive characterization tool for many LANL missions. Contrast in conventional radiography results from attenuation of the incoming x-ray or neutron beam by the object. Neutrons have a great benefit in detecting light elements (e.g. hydrogen) in the presence of heavier elements and penetrate deeper than X-rays into many materials, but neutron radiography resolution is typically limited to ~50 μm. Cracks, voids, pores and a variety of other features smaller than this resolution are therefore undetectable in attenuation based neutron imaging. However, novel neutron imaging modalities leveraging off of interferometric methods, so-called neutron grating interferometry (NGI), are able to spatially map sub-micron features and interfacial features while also exploiting the neutron’s sensitivity to light elements and isotope specific contrast to enable material characterization otherwise impossible.

36 MATERIALS SCIENCE↗

Con Connections: Detecting Fraud from Abstracts using Topological Data Analysis

In this paper we present a novel approach for identifying fraudulent papers from their titles and abstracts. The premise of the approach is that there are holes in the presentation of the approach and findings of fraudulent research papers. As an abstract is intended to highlight key features of the approach as well as important conclusions the authors seek to determine if the assumed existence of holes can be identified from analysis of abstracts alone. The data set considered is derived from papers sharing a single author with labels determined based on a formal linguistic analysis of the complete documents. To detect these logical and literary holes we utilize techniques from topological data analysis which summarizes data based on the presence of multi-dimensional, topological holes. We find that, in fact, topological features derived through a combination of techniques in natural language processing and time-series analysis allow for superior detection of the fraudulent papers than the natural language processing tools alone. Thus we conclude that the connections and holes present in the abstracts of research cons contributes to an ability to infer the scientific validity of the corresponding work.

Tymochko, Sarah J.↗

Spatial Replication Is Important for Developing Landscape Genetic Inferences for a Wetland Salamander

Habitat fragmentation is a pressing threat to wildlife populations, and maintenance of gene flow between populations is an essential goal of conservation. Resistance surfaces have emerged as an important tool for modelling connectivity and developing management strategies to mitigate effects of habitat fragmentation. However, recent studies have noted inconsistencies in the factors most strongly associated with connectivity across different landscapes. Thus, replication of genetic-based resistance surface optimisation across landscapes may be necessary for making robust conclusions about the influence of environmental variables. Accordingly, replication represents a substantive challenge and opportunity in the field of landscape genetics. In this study, we conducted replicated landscape genetic analyses across five landscapes in Tennessee and Kentucky for a threatened wetland amphibian, the four-toed salamander (Hemidactylium scutatum). We tested multiple hypotheses of how different landscape features that could directly affect small, desiccation-intolerant amphibians (e.g., canopy cover) influenced gene flow and assessed the appropriate scale at which to model different features. We found some concordance in the landscape features that influenced gene flow (e.g., a common importance of forest cover and topography), but also some differences—potentially owing to the difference in variability of predictors across landscapes. We also found discordance in the scale of effect of different features across landscapes. In conclusion, our work emphasises that flat areas of moist forest not bisected by roads may be important for H. scutatum conservation, and our replicated design allows us to identify relationships that would have been missed if only using one study site.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of different manufacturing methods on polyamide reverse-osmosis membranes for desalination: Insights from molecular dynamics simulations

Membranes are a key technology platform for a broad application of energy-efficient separations. To best serve the separation demands of industry, the manufacturing processes for these membranes are garnering increasing attention. In particular, for water desalination, the industry leading polyamide (PA) reverse osmosis (RO) membranes can be manufactured via molecular layer-by-layer (mLBL) deposition, interfacial polymerization (IP), and 3D-printing technique. However, the influence of different manufacturing methods on PA membrane’s properties is far from understood. Here, in this study, we present the high-pressure transport behavior of water and salt ions for PA membranes formed with IP, mLBL, and 3D-printing through non-equilibrium molecular dynamics simulations. Studies show that membranes fabricated with 3D-printing have similar performances to those manufactured using mLBL, quantified by water permeability, rejection of salt ions, structural integrity, and porosity features. However, the membranes formed with IP exhibit faster water transport, lower rejection, worse structural integrity, and more inhomogeneous network pores than those constructed using mLBL and 3D-printing. The unconnected water-accessible space governs water transport for PA membranes formed with mLBL and 3D-printing, which offers the impermanent open-closed pores that enable water to jump through PA membranes. In contrast, the permeated water-enterable space plays a prominent role in water movement across the PA membrane formed with IP, providing a continuous transport channel at high pressure. Importantly, we observe the more significant compaction features at high pressure for PA membranes formed with IP than mLBL and 3D printing. In short, these findings provide a comprehensive understanding of existing membrane preparation technologies. It also provides a guide for developing the new membrane preparation process at the molecular level.

3D-printing↗

Drivers of Natural Variation in Water-Use Efficiency Under Fluctuating Light Are Promising Targets for Improvement in Sorghum

Improving leaf intrinsic water-use efficiency ( iWUE ), the ratio of photosynthetic CO 2 assimilation to stomatal conductance, could decrease crop freshwater consumption. iWUE has primarily been studied under steady-state light, but light in crop stands rapidly fluctuates. Leaf responses to these fluctuations substantially affect overall plant performance. Notably, photosynthesis responds faster than stomata to decreases in light intensity: this desynchronization results in substantial loss of iWUE . Traits that could improve iWUE under fluctuating light, such as faster stomatal movement to better synchronize stomata with photosynthesis, show significant natural diversity in C 3 species. However, C 4 crops have been less closely investigated. Additionally, while modification of photosynthetic or stomatal traits independent of one another will theoretically have a proportionate effect on iWUE , in reality these traits are inter-dependent. It is unclear how interactions between photosynthesis and stomata affect natural diversity in iWUE , and whether some traits are more tractable drivers to improve iWUE . Here, measurements of photosynthesis, stomatal conductance and iWUE under steady-state and fluctuating light, along with stomatal patterning, were obtained in 18 field-grown accessions of the C 4 crop sorghum. These traits showed significant natural diversity but were highly correlated, with important implications for improvement of iWUE . Some features, such as gradual responses of photosynthesis to decreases in light, appeared promising for improvement of iWUE . Other traits showed tradeoffs that negated benefits to iWUE , e.g., accessions with faster stomatal responses to decreases in light, expected to benefit iWUE , also displayed more abrupt losses in photosynthesis, resulting in overall lower iWUE . Genetic engineering might be needed to break these natural tradeoffs and achieve optimal trait combinations, e.g., leaves with fewer, smaller stomata, more sensitive to changes in photosynthesis. Traits describing iWUE at steady-state, and the change in iWUE following decreases in light, were important contributors to overall iWUE under fluctuating light.

54 ENVIRONMENTAL SCIENCES↗

Evolution of Idealized Vortices in Monsoon-Like Shears: Application to Monsoon Depressions

Abstract This study examines processes fundamental to the development of South Asian monsoon depressions using an array of integrations of an idealized convection-permitting numerical model. In each integration, a wave of initially small amplitude is subjected to a different amount of vertical and meridional wind shear, with temperature and moisture fields constructed according to realistic constraints. Based on the evolution of this disturbance into monsoon depression–like vortices, two features of the background environment emerge as important: the low-level gradient of moist static energy (MSE) and the low-level meridional shear. As the low-level MSE gradient steepens, the disturbance becomes stronger and produces more rain. This strengthening results from the interaction of the vortex with latent heat release by convection that is in turn organized by positive MSE advection in the northerly flow west of the vortex. In this region of advection, moister air from the north ascends along upward-sloping isentropes, driving moist convection. The disturbance also becomes stronger with increasing meridional shear, which makes the environment more barotropically unstable. The absence of either of these two features of the background environment prevents substantial growth of the disturbance. Our results suggest that monsoon depression growth in South Asia is fostered by the coexistence of a strong low-level MSE gradient with strong meridional wind shear associated with the monsoon trough.

54 ENVIRONMENTAL SCIENCES↗

Faceted NiO(111) nanosheets: morphological and catalytic evolution for the oxygen evolution reaction

The renaissance of the energy system through the use of green hydrogen by water electrolysis lies behind the development of abundant, active, and scalable catalysts for the oxygen evolution reaction (OER). A fundumental understanding of the surface properties for these materials is of vital importance in producing viable heterogenous catalysts. In this feature article, we summarize several years of collaborative work on a uniquely faceted NiO(111) nanosheet possessing hexagonal holes with a focus on understanding how the evolution of the catalyst surface and bulk composition effects OER performance. The importance of surface faceting, morphological evolution, and metal combination by different doping strategies are all analyzed and summarized to further improve the material's performance. Furthermore, microwave and supercritical synthesis processes are utilized to understand how varying wet-chemical techniques effect the formation of the NiO(111) nanosheet and activity of the material. We discuss our chosen strategies and the difficulties encountered with optimizing a catalyst surface for the OER.

08 HYDROGEN↗

Fault Characterization and Diagnostics Supporting Condition-Based Operation and Maintenance of Gas Turbine Engines

Condition-Based Operation and Maintenance (CBOM) is the state-of-the-art in maintenance approaches for gas turbine engines. CBOM applies engine sensor information to the optimization of future operation and maintenance procedures; this technique reduces costs for engine operators by minimizing unplanned outages and catastrophic engine degradation. However, due to the complexities of gas turbine operation and the lack of available engine sensors, further development is required to fully realize the benefits of CBOM. In the turbine section, rotating components interact with high temperature flows, which creates intense thermal and mechanical stresses. As a result, there are numerous mechanisms of component degradation in the turbine section. Furthermore, turbine components – like stator vanes and rotor blades – are among the most expensive in the engine because they are complex to design and manufacture. For these reasons, this dissertation addresses two main questions: (i) which parameters or faults within the turbine section are most important to monitor, and (ii) how can these parameters or faults be monitored in an engine-relevant environment? Although many turbine parameters and faults have been investigated in the open literature, there are some faults that are still not well understood. Rotor-casing eccentricity, which causes a non-constant blade tip clearance around the annulus, has not been investigated in terms of its effects on turbine efficiency. Therefore, the first study in this dissertation quantifies overall and local turbine efficiency for varying levels of rotor-casing eccentricity. Results showed negligible variations to overall turbine efficiency, meaning rotor-casing eccentricity only becomes relevant to CBOM when its severity causes rotordynamic issues. Purge flow is critical to turbine hardware longevity because it prevents ingestion of hot main gas path (MGP) flow into the under-platform regions. Despite its importance, there are currently no methods for monitoring purge flow performance in an engine environment. Therefore, the second study in this dissertation develops a predictive model for sealing effectiveness using inputs from two fast-response pressure sensors. Results exhibited low prediction errors across a full range of purge flow rates, which supports the viability of the modelling approach for CBOM. The final two studies in this dissertation address blade coolant flow monitoring. This cooling flow is responsible for protecting the turbine blades from the MGP flow, which exits the combustor at temperatures greater than the blade melting point. These studies showed that temperature measurements on the blade surface can be used to accurately predict blade coolant flow rate, and that defining the candidate features relative to the coolant trajectory is important for maintaining accuracy as coolant flow rate degradation occurs. This work enables blade coolant flow monitoring, which is currently not possible through existing condition monitoring techniques.

condition-based, gas turbines, diagnostics,↗

Kinematic Variables and Feature Engineering for Particle Phenomenology

Kinematic variables have been playing an important role in collider phenomenology, as they expedite discoveries of new particles by separating signal events from unwanted background events and allow for measurements of particle properties such as masses, couplings, spins, etc. For the past 10 years, an enormous number of kinematic variables have been designed and proposed, primarily for the experiments at the Large Hadron Collider, allowing for a drastic reduction of high-dimensional experimental data to lower-dimensional observables, from which one can readily extract underlying features of phase space and develop better-optimized data-analysis strategies. We review these recent developments in the area of phase space kinematics, summarizing the new kinematic variables with important phenomenological implications and physics applications. We also review recently proposed analysis methods and techniques specifically designed to leverage the new kinematic variables. As machine learning is nowadays percolating through many fields of particle physics including collider phenomenology, we discuss the interconnection and mutual complementarity of kinematic variables and machine learning techniques. We finally discuss how the utilization of kinematic variables originally developed for colliders can be extended to other high-energy physics experiments including neutrino experiments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Spatiotemporal distribution of chemical signatures exhibited by Myxococcus xanthus in response to metabolic conditions

Myxococcus xanthus is a common soil bacterium with a complex life cycle, which is known for production of secondary metabolites. However, little is known about the effects of nutrient availability on M. xanthus metabolite production. In this study, we utilize confocal Raman microscopy (CRM) to examine the spatiotemporal distribution of chemical signatures secreted by M. xanthus and their response to varied nutrient availability. Here, ten distinct spectral features are observed by CRM from M. xanthus grown on nutrient-rich medium. However, when M. xanthus is constrained to grow under nutrient-limited conditions, by starving it of casitone, it develops fruiting bodies, and the accompanying Raman microspectra are dramatically altered. The reduced metabolic state engendered by the absence of casitone in the medium is associated with reduced, or completely eliminated, features at 1140 cm –1 , 1560 cm –1 , and 1648 cm –1 . In their place, a feature at 1537 cm –1 is observed, this feature being tentatively assigned to a transitional phase important for cellular adaptation to varying environmental conditions. In addition, correlating principal component analysis heat maps with optical images illustrates how fruiting bodies in the center co-exist with motile cells at the colony edge. While the metabolites responsible for these Raman features are not completely identified, three M. xanthus peaks at 1004, 1151, and 1510 cm –1 are consistent with the production of lycopene. Thus, a combination of CRM imaging and PCA enables the spatial mapping of spectral signatures of secreted factors from M. xanthus and their correlation with metabolic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of weak interlayer coupling in ultrafast exciton-exciton annihilation in two-dimensional rhenium dichalcogenides

Strong interactions between excitons are a characteristic feature of two-dimensional (2D) semiconductors, determining important excitonic properties, such as exciton lifetime, coherence, and photon-emission efficiency. Rhenium disulfide (ReS 2 ), a member of the 2D transition-metal dichalcogenide (TMD) family, has recently attracted great attention due to its unique excitons that exhibit excellent polarization selectivity and coherence features. However, an in-depth understanding of exciton-exciton interactions in ReS 2 is still lacking. In this work, we used ultrafast pump-probe spectroscopy to study exciton-exciton interactions in monolayer (1L), bilayer (2L), and triple layer ReS 2 . Additionally, we directly measure the rate of exciton-exciton annihilation, a representative Auger-type interaction between excitons. It decreases with increasing layer number, as observed in other 2D TMDs. However, while other TMDs exhibit a sharp weakening of exciton-exciton annihilation between 1L and 2L, such behavior was not observed in ReS 2 . We attribute this distinct feature in ReS 2 to the relatively weak interlayer coupling, which prohibits a substantial change in the electronic structure when the thickness varies. This work not only highlights the unique excitonic properties of ReS 2 but also provides novel insight into the thickness dependence of exciton-exciton interactions in 2D systems.

36 MATERIALS SCIENCE↗

Predicting initial dissolution rates using structural features from molecular dynamics simulations

Predicting chemical durability of glass materials is important for various applications from daily life such as drink glass and kitchen ware to advanced technologies such as nuclear waste disposal and biomedicine. In this work, we explored prediction of initial dissolution rate through structural features from molecular dynamics (MD) simulations for a wide range of glass compositions (total 28) including borosilicate and aluminosilicate glasses, ZrO 2 -containing and V 2 O 5 -containing boroaluminosilicate glasses. The initial dissolution rates (r 0 ) measured experimentally at 90 °C with varying solution conditions were correlated with structural features (e.g., polyhedral linkages and non-bridging oxygen species) obtained from MD simulations, either from this study or from literature. Since hydrolysis of the glass network through breaking of the network former linkages (e.g., Si-O-Si, Si-O-Al, etc.) is a critical step of network glass dissolution, the statistics of these linkages obtained from MD were correlated to r0 through linear regression, where the coefficient of determination (R 2 ) and root mean square error are found to be 0.949 and 0.681, respectively. This model was compared and discussed with existing models developed by various approaches including machine learning, the kinetic rate equation, topological constraint theory, and other descriptors from MD simulations. The discussion provides insights on future model improvements to predict glass dissolution. In addition, the impact of V 2 O 5 on the glass dissolution was examined in detail, implicating that the impact is not the same across all glass compositions and test conditions.

36 MATERIALS SCIENCE↗

Ascribe XR v0.1.0

Ascribe XR is an immersive visualization software designed for scientists and engineers working with 3D data sets. Its key features include interactive exploration, multi-user collaboration, and flexible data import capabilities, supporting various formats such as meshes, volumes, and terrain maps. The software utilizes Godot, OpenXR and PC-VR technology to provide an immersive experience. Ascribe XR is used for data analysis, visualization, and collaboration in various fields, enabling users to gain deeper insights into complex data sets. Its advantages over similar technologies include its flexibility, customizability, and ease of use. Ascribe XR's interactive and immersive environment facilitates collaboration and accelerates the discovery process. Compared to traditional 2D visualization tools, Ascribe XR offers a more engaging and intuitive experience, allowing users to explore complex data sets in a more natural and interactive way. Its ability to support multi-user collaboration and flexible data import capabilities make it a versatile tool for various applications. Overall, Ascribe XR provides a unique combination of features, usability, and performance, making it an attractive solution for scientists and engineers working with 3D data sets.

Pandolfi, Ronald [Lawrence Berkeley National Labor↗

Short-term apartment-level load forecasting using a modified neural network with selected auto-regressive features

Residential electricity load profiles and their diversity have become increasingly important to realize the benefits of Smart or Transactive Energy Networks (TENs). An important element of TENs will be practical, accurate, and implementable residential load forecasting techniques. While there have been many approaches to short-term load forecasting, few have included forecasting for individual households, partly because the high volatility and idiosyncrasies present in individual household load data can pose significant challenges. In this study, we develop a Convolutional Long Short-Term Memory-based neural network with Selected Autoregressive Features (termed a CLSAF model) to improve short-term household electricity load forecasting accuracy by employing three strategies: autoregressive features selection, exogenous features selection, and a “default” state to avoid overfitting at times of high load volatility. We include aggregations of apartments to floor and building level, because utilities may favor transactive approaches that rely on aggregator models, e.g., a cluster of consumers as opposed to an individual. We demonstrate that the CLSAF model, by virtue of its enhanced feature representation and modest computational resources, can accomplish load forecasting in a multi-family residential building across three spatial granularities (individual apartment/household, floor, and building levels), with an accuracy improvement of up to 25% compared to a persistence model. We propose a data screening technique to characterize time-series electricity-load data. This technique is suitable for integration into a TEN ecosystem and allows one to estimate confidence levels of the load forecasts to optimize computational resources and the risks associated with uncertain forecasts.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Recent Advances in Scalable, High‐Mass Loaded Electrodes for Grid‐Scale Energy Storage

Abstract The increasing electrification of daily life as well as the intermittent characteristic of renewable energy sources require viable solutions for grid‐scale energy storage. Critical considerations for grid storage applications are electrode mass loading and electrode thickness as these features govern battery pack energy density, an important factor in determining manufacturing costs. For this reason, there is increased interest in finding new ways of creating electrodes with high mass loading. In this review, various high‐mass loading fabrication approaches are considered for positive electrode materials used in batteries. The benchmark used for high mass loading is above 20 mg cm −2 , which is higher than the practical limit of conventional tape‐cast electrodes. Several different electrode approaches are described including templating, laser patterning, direct ink writing, and electrodeposition. A variety of materials are covered with the most prominent being LiFe(PO 4 ) (LFP), LiCoO 2 (LCO), and MnO 2 . In research to date, scalable electrochemical performance has been achieved with mass loadings over 100 mg cm −2 . Areal capacities as high as 14.7 mAh cm −2 at 1.82 mA cm −2 have been achieved in non‐aqueous electrolytes and 9.8 mAh cm −2 at 10 mA cm −2 in aqueous electrolytes. These results establish that the mass loading of electrodes can be scaled up without compromising their electrochemical properties.

White, Makena [Department of Materials Science and↗