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Results for “analytical detection method”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

A comparison of machine learning methods to classify radioactive elements using prompt-gamma-ray neutron activation data

The detection of illicit radiological materials is critical to establishing a robust second line of defence in nuclear security. Neutron-capture prompt-gamma activation analysis (PGAA) can be used to detect multiple radioactive materials across the entire Periodic Table. However, long detection times and a high rate of false positives pose a significant hindrance in the deployment of PGAA-based systems to identify the presence of illicit substances in nuclear forensics. In the present work, six different machine-learning algorithms were developed to classify radioactive elements based on the PGAA energy spectra. The model performance was evaluated using standard classification metrics and trend curves with an emphasis on comparing the effectiveness of algorithms that are best suited for classifying imbalanced datasets. We analyse the classification performance based on Precision, Recall, F1-score, Specificity, Confusion matrix, ROC-AUC curves, and Geometric Mean Score (GMS) measures. The tree-based algorithms (Decision Trees, Random Forest and AdaBoost) have consistently outperformed Support Vector Machine and K-Nearest Neighbours. Based on the results presented, AdaBoost is the preferred classifier to analyse data containing PGAA spectral information due to the high recall and minimal false negatives reported in the minority class.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

High-throughput Li plating quantification for fast-charging battery design

Fast charging of most commercial lithium-ion batteries is limited due to fear of lithium plating on the graphite anode, which is difficult to detect and poses considerable safety risk. In this report we demonstrate the power of simple, accessible and high-throughput cycling techniques to quantify irreversible Li plating spanning data from over 200 cells. We first observe the effects of energy density, charge rate, temperature and state of charge on lithium plating, use the results to refine a mature physics-based electrochemical model and provide an interpretable empirical equation for predicting the plating onset state of charge. We then explore the reversibility of lithium plating and its connection to electrolyte design for preventing irreversible Li accumulation. Finally, we design a method to quantify in situ Li plating for commercially relevant graphite|LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC) cells and compare with results from the experimentally convenient Li|graphite configuration. The hypotheses and abundant data herein were generated primarily with equipment universal to the battery researcher, encouraging further development of innovative testing methods and data processing that enable rapid battery engineering.

25 ENERGY STORAGE↗
DOE OSTI2024

Assessment of two benzylation strategies for the analysis of nerve-agent derived ethyl- and pinacolyl methyl phosphonic acids in sandy loam soil by GC–MS

Despite their prohibition by the Chemical Weapons Convention, nerve agents (NAs) remain in use against military and civilian targets. Due to their high reactivity, NAs readily degrade to phosphonic acids, making them important markers in the inspection of areas of presumed NA use. In this work, we assess the use of benzylation to modify ethyl- and pinacolyl methylphosphonic acids, degradation products of VX and Soman respectively, for their efficient detection in a soil matrix at ~10 and ~1 μg/g using GC–MS. The soil matrix, Sandy Loam (SL), was chosen for its ubiquitous nature, complex composition with silica particles embedded in clay, and low organic content. In this study, we demonstrate that benzylation via benzyl bromide yields a LOD = 25.6 ng/mL for benzylated-EMPA and LOD = 30.1 ng/mL for benzylated-PMPA. This is superior to the use of p-methoxybenzyl trichloroacetimidate in providing stable phosphonic acid ester derivatives for analysis. A base-modified procedure for p-methoxybenzylation was explored in this study yielding a LOD = 29.1 ng/mL for p-methoxybenzylated-EMPA and LOD = 39.8 ng/mL for p-methoxybenzylated-PMPA. Both benzylation pathways (benzyl bromide and p-methoxybenzyl trichloroacetimidate) can be used to yield phosphonic acid derivatives that provide further confirmation of these Soman and VX degradation products in soil samples in investigative scenarios. The work herein represents the first application of benzylation methods for the analysis of these NA markers in the acidic, silicon-based SL soil.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Inference of the optical depth to reionization τ from Planck CMB maps with convolutional neural networks

The optical depth to reionization, τ, is the least constrained parameter of the cosmological Λ cold dark matter (ΛCDM) model. To date, its most precise value is inferred from large-scale polarized cosmic microwave background (CMB) power spectra from the High Frequency Instrument (HFI) aboard the Planck satellite. These maps are known to contain significant contamination by residual non-Gaussian systematic effects, which are hard to model analytically. Therefore, robust constraints on τ are currently obtained through an empirical cross-spectrum likelihood built from simulations. In this paper, we present a likelihood-free inference of τ from polarized Planck HFI maps which, for the first time, is fully based on neural networks (NNs). NNs have the advantage of not requiring an analytical description of the data and can be trained on state-of-the-art simulations, combining the information from multiple channels. By using Gaussian sky simulations and Planck SRoll2 simulations, including CMB, noise, and residual instrumental systematic effects, we trained, tested, and validated NN models considering different setups. We inferred the value of τ directly from Stokes Q and U maps at ~4° pixel resolution, without computing angular power spectra. On Planck data, we obtained τ NN = 0.0579 ± 0.0082, which is compatible with current EE cross-spectrum results but with a ~30% larger uncertainty, which can be assigned to the inherent nonoptimality of our estimator and to the retraining procedure applied to avoid biases. While this paper does not improve on current cosmological constraints on τ, our analysis represents a first robust application of NN-based inference on real data, and highlights its potential as a promising tool for complementary analysis of near-future CMB experiments, also in view of the ongoing challenge to achieve the first detection of primordial gravitational waves.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Investigating Cu-Site Doped Cu–Sb–S Nanoparticles Using Photoelectron and Electron Paramagnetic Resonance Spectroscopy

Tetrahedrite (Cu 12 Sb 4 S 13 ) and famatinite (Cu 3 SbS 4 ) are good candidates for green energy applications because they possess promising thermoelectric and photovoltaic properties as well as contain earth-abundant and nontoxic constituents. Herein, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and electron paramagnetic resonance spectroscopy (EPR) methods examined inherent electronic properties and interatomic magnetic interactions of Cu-site doped tetrahedrite and famatinite nanomaterials. An energy-efficient modified polyol method was utilized for the synthesis of tetrahedrite and famatinite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, and Co. This is the first parallel study of tetrahedrite and famatinite nanomaterials with XPS, UPS, and EPR methods alongside a systematic analysis of dopant-dependent effects on the electronic structure and magnetic interactions for each material. XPS showed that the Cu and Sb species in tetrahedrite and famatinite possess different oxidation states, while UPS characterization reveals larger dopant-dependent shifts in the work function for tetrahedrite nanoparticles (4.21 to 4.79 eV) than for famatinite nanoparticles (4.57 to 4.77 eV). Finally, all famatinite nanoparticles display an EPR signal, indicating trace amounts of paramagnetic Cu(II) present below the detection limit of XPS. For tetrahedrite, EPR signatures were observed only for the Zn-doped and Mn-doped nanoparticles, suggesting signal broadening from Cu–Cu spin exchange or spin–lattice relaxation. This study demonstrates the complementary nature of XPS and EPR techniques for studying the oxidation states of metals in solid-state nanomaterials. Comparing the electronic and magnetic properties of tetrahedrite and famatinite while studying the impact of dopant incorporation will guide future endeavors in designing sustainable, high-performance materials for renewable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The Hubble PanCET Program: A Metal-rich Atmosphere for the Inflated Hot Jupiter HAT-P-41b

We present a comprehensive analysis of the 0.3–5 μm transit spectrum for the inflated hot Jupiter HAT-P-41b. The planet was observed in transit with Hubble STIS and WFC3 as part of the Hubble Panchromatic Comparative Exoplanet Treasury (PanCET) program, and we combine those data with warm Spitzer transit observations. We extract transit depths from each of the data sets, presenting the STIS transit spectrum (0.29–0.93 μm) for the first time. We retrieve the transit spectrum both with a free-chemistry retrieval suite (AURA) and a complementary chemical equilibrium retrieval suite (PLATON) to constrain the atmospheric properties at the day–night terminator. Both methods provide an excellent fit to the observed spectrum. Both AURA and PLATON retrieve a metal-rich atmosphere for almost all model assumptions (most likely O/H ratio of log{sub 10}Z/Z{sub ⊙}=1.46{sub −0.68}{sup +0.53} and log{sub 10}Z/Z{sub ⊙}=2.33{sub −0.25}{sup +0.23}, respectively); this is driven by a 4.9σ detection of H{sub 2}O as well as evidence of gas absorption in the optical (>2.7σ detection) due to Na, AlO, and/or VO/TiO, though no individual species is strongly detected. Both retrievals determine the transit spectrum to be consistent with a clear atmosphere, with no evidence of haze or high-altitude clouds. Interior modeling constraints on the maximum atmospheric metallicity (log{sub 10}Z/Z{sub ⊙}<1.7) favor the AURA results. The inferred elemental oxygen abundance suggests that HAT-P-41b has one of the most metal-rich atmospheres of any hot Jupiters known to date. Overall, the inferred high metallicity and high inflation make HAT-P-41b an interesting test case for planet formation theories.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Deep Learning for In-Situ Layer Quality Monitoring during Laser-Based Directed Energy Deposition (LB-DED) Additive Manufacturing Process

Defects are a leading issue for the rejection of parts manufactured through the Directed Energy Deposition (DED) Additive Manufacturing (AM) process. In an attempt to illuminate and advance in situ quality monitoring and control of workpieces, we present an innovative data-driven method that synchronously collects sensing data and AM process parameters with a low sampling rate during the DED process. The proposed data-driven technique determines the important influences that individual printing parameters and sensing features have on prediction at the inter-layer qualification to perform feature selection. Three Machine Learning (ML) algorithms including Random Forest (RF), Support Vector Machine (SVM), and Convolutional Neural Network (CNN) are used. During post-production, a threshold is applied to detect low-density occurrences such as porosity sizes and quantities from CT scans that render individual layers acceptable or unacceptable. This information is fed to the ML models for training. Training/testing are completed offline on samples deemed “high-quality” and “low-quality”, utilizing only features recorded from the build process. CNN results show that the classification of acceptable/unacceptable layers can reach between 90% accuracy while training/testing on a “high-quality” sample and dip to 65% accuracy when trained/tested on “low-quality”/“high-quality” (respectively), indicating over-fitting but showing CNN as a promising inter-layer classifier.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Mineralogical, magnetic and geochemical data constrain the pathways and extent of weathering of mineralized sedimentary rocks

The oxidative weathering of sulfidic rock can profoundly impact watersheds through the resulting export of acidity and metals. Weathering leaves a record of mineral transformation, particularly involving minor redox-sensitive phases, that can inform the development of conceptual and quantitative models. In sulfidic sedimentary rocks, however, variations in depositional history, diagenesis and mineralization can change or overprint the distributions of these trace minerals, complicating the interpretation of weathering signatures. Here we show that a combination of bulk mineralogical and geochemical techniques, micrometer-resolution X-ray fluorescence microprobe analysis and rock magnetic measurements, applied to drill core samples and single weathered fractures, can provide data that enable the development of a geochemically consistent weathering model. This work focused on one watershed in the Upper Colorado River Basin sitting within the Mesaverde Formation, a sedimentary sandstone bedrock with disseminated sulfide minerals, including pyrite and sphalerite, that were introduced during diagenesis and subsequent magmatic-hydrothermal mineralization. Combined analytical methods revealed the pathways of iron (Fe), carbonate and silicate mineral weathering and showed how pH controls element retention or release from the actively weathering fractured sandstone. Drill core logging, whole rock X-ray diffraction, and geochemical measurements document the progression from unweathered rock at depth to weathered rock at the surface. X-ray microprobe analyses of a 1-cm size weathering profile along a fracture surface are consistent with the mobilization of Fe(II) and Fe(III) into acidic pore water from the dissolution of primary pyrite, Fe-sphalerite, chlorite, and minor siderite and pyrrhotite. These reactions are followed by the precipitation of secondary minerals such as of goethite and jarosite, a Fe-(oxyhydr)oxide and hydrous Fe(III) sulfate, respectively. Microscale analyses also helped explain the weathering reactions responsible for the mineralogical transformations observed in the top and most weathered section of the drill core. For example, dissolution of feldspar and chlorite neutralizes the acidity generated by Fe and sulfide mineral oxidation, oversaturating the solution in both Fe-oxides. The combination of X-ray spectromicroscopy and magnetic measurements show that the Fe(III) product is goethite, mainly present either as a coating on fracture surfaces in the actively weathering region of the core or more homogeneously contained within the unconsolidated regolith at the top of the core. Low-temperature magnetic data reveal the presence of ferromagnetic Fe-sulfide pyrrhotite that, although it occurs at trace concentrations, could provide a qualitative proxy for unweathered sulfide minerals because the loss of pyrrhotite is associated with the onset of oxidative weathering. Pyrrhotite loss and goethite formation are detectable through room-temperature magnetic coercivity changes, suggesting that rock magnetic measurements can determine weathering intensity in rock samples at many scales. In conclusion, this work contributes evidence that the weathering of sulfidic sedimentary rocks follows a geochemical pattern in which the abundance of sulfide minerals controls the generation of acidity and dissolved elements, and the pH-dependent mobility of these elements controls their export to the ground- and surface-water.

58 GEOSCIENCES↗
DOE OSTI2020

Reaction mechanisms of a cyclic ether intermediate: Ethyloxirane

Oxiranes are a class of cyclic ethers formed in abundance during low-temperature combustion of hydrocarbons and biofuels, either via chain-propagating steps that occur from unimolecular decomposition of β -hydroperoxyalkyl radicals ( β -˙QOOH) or from reactions of HOÓ with alkenes. Ethyloxirane is one of four alkyl-substituted cyclic ether isomers produced as an intermediate from n -butane oxidation. While rate coefficients for β -˙QOOH → ethyloxirane + ÓH are reported extensively, subsequent reaction mechanisms of the cyclic ether are not. As a result, chemical kinetics mechanisms commonly adopt simplified chemistry to describe ethyloxirane consumption by convoluting several elementary reactions into a single step, which may introduce mechanism truncation error—uncertainty derived from missing or incomplete chemistry. Here we provide fundamental insight on reaction mechanisms of ethyloxirane in support of ongoing efforts to minimize mechanism truncation error. Reaction mechanisms are inferred from the detection of products during chlorine atom-initiated oxidation experiments using multiplexed photoionization mass spectrometry conducted at 10 Torr and temperatures of 650 K and 800 K. To complement the experiments, calculations of stationary point energies were conducted using the ccCA-PS3 composite method on ˙R + O 2 potential energy surfaces for the four ethyloxiranyl radical isomers, which produced barrier heights for 24 reaction pathways. In addition to products from ˙QOOH → cyclic ether + ÓH and ˙R + O 2 → conjugate alkene + HOÓ, both of which were significant pathways and are prototypical to alkane oxidation, other species were identified from ring-opening of both ethyloxiranyl and ˙QOOH radicals. The latter occurs when the unpaired electron is localized on the ether group, causing the initial ˙QOOH structure to ring-open and form a resonance-stabilized ketohydroperoxide-type radical. The present work provides the first analysis of ethyloxirane oxidation chemistry, which reveals that consumption pathways are complex and may require an expansion of submechanisms to increase the fidelity of chemical kinetics mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

X-Ray Induced Chemical Reaction Revealed by In Situ X-Ray Diffraction and Scanning X-Ray Microscopy in 15 nm Resolution

The detection sensitivity of synchrotron-based X-ray techniques has been largely improved due to the ever-increasing source brightness, which has significantly advanced ex situ and in situ research for energy materials such as lithium-ion batteries. However, the strong beam–material interaction arising from the high beam flux can substantially modify the material structure. The beam-induced parasitic effect inevitably interferes with the intrinsic material property, making the interpretation of the experimental results difficult and requiring comprehensive assessments. Here, we present a quantitative study of the beam effect on an electrode material Ag 2 VO 2 PO 4 using four different X-ray characterization methods with different radiation dose rates. The material system exhibits interesting and reversible radiation-induced thermal and chemical reactions, further evaluated under electron microscopy to illustrate the underlying mechanism. Further, the work will provide a guideline for using synchrotron X-rays to distinguish the intrinsic behavior from extrinsic structure change of materials induced by X-rays.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Assessment and Non-Destructive Evaluation of the Influence of Residual Solvent on a Two-Part Epoxy-Based Adhesive Using Ultrasonics

Polymers are increasingly being used in higher demanding applications due to their ability to tailor the properties of structures while allowing for a weight and cost reduction. Solvents play an important role in the manufacture of polymeric structures since they allow for a reduction in the polymer’s viscosity or assist with the dispersion of fillers into the polymer matrix. However, the incorrect removal of the solvent affects both the physical and chemical properties of polymeric materials. The presence of residual solvent can also negatively affect the curing kinetics and the final quality of polymers. Destructive testing is mainly performed to characterize the properties of these materials. However, this type of testing involves using lab-type equipment that cannot be taken in-field to perform in situ testing and requires a specific sample preparation. Here, a method is presented to non-destructively evaluate the curing process and final viscoelastic properties of polymeric materials using ultrasonics. In this study, changes in longitudinal sound speed were detected during the curing of an aerospace epoxy adhesive as a result of variations in polymer chemistry. To simulate the presence of residual solvent, samples containing different weight percentages of isopropyl alcohol were manufactured and tested using ultrasonics. Thermogravimetric analysis was used to show changes in the decomposition of the adhesive due to the presence of IPA within the polymer structure. Adding 2, 4, and 6 wt.% of IPA decreased the adhesive’s lap shear strength by 40, 58, and 71%, respectively. Ultrasonics were used to show how the solvent influenced the curing process and the final sound speed of the adhesive. Young’s modulus and Poisson’s ratio were determined using both the longitudinal and shear sound speeds of the adhesive. Using ultrasonics has the potential to non-invasively characterize the quality of polymers in both an in-field and manufacturing settings, ensuring their reliability during use in demanding applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Proton-detected solid-state NMR spectroscopy of spin-1/2 nuclei with large chemical shift anisotropy

Constant-time (CT) dipolar heteronuclear multiple quantum coherence (D-HMQC) has previously been demonstrated as a method for proton detection of high-resolution wideline NMR spectra of spin-1/2 nuclei with large chemical shift anisotropy (CSA). However, 1 H transverse relaxation and t 1 -noise often reduce the sensitivity of D-HMQC experiments, preventing the theoretical gains in sensitivity provided by 1 H detection from being realized. In this paper, we demonstrate a series of improved pulse sequences for 1 H detection of spin-1/2 nuclei under fast MAS, with 195 Pt SSNMR experiments on cisplatin as an example. First, a t 1 -incrementation protocol for D-HMQC dubbed Arbitrary Indirect Dwell (AID) is demonstrated. AID allows the use of arbitrary, rotor asynchronous t 1 -increments, but removes the constant time period from CT D-HMQC, resulting in improved sensitivity by reducing transverse relaxation losses. Next, we show that short high-power adiabatic pulses (SHAPs), which efficiently invert broad MAS sideband manifolds, can be effectively incorporated into 1 H detected symmetry-based resonance echo double resonance (S-REDOR) and t 1 -noise eliminated (TONE) D-HMQC experiments. The S-REDOR experiments with SHAPs provide approximately double the dipolar dephasing, as compared to experiments with rectangular inversion pulses. We lastly show that sensitivity and resolution can be further enhanced with the use of swept excitation pulses as well as adiabatic magic angle turning (aMAT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

WISP: Watching grid Infrastructure Stealthily through Proxies (Final Technical Report)

The complex interdependencies of cyber systems (sensors and communications), physical grids and associated electricity market operations make protecting electric power grids a significant challenge. The energy sector is constantly under new, targeted, advanced and dangerous cyber-attacks that have the potential to result in the loss of human life. These threats are further exacerbated by our need to modernize the grid. One focus of cyber security research in smart grids is the securing of the SCADA system through advanced intrusion detection systems (IDS) and bad data detection algorithms in state estimation. These methods either require full knowledge of the system topology and parameters or fail to understand the physical behaviors under attack. WISP (Watching grid Infrastructure Stealthily through Proxies) is designed to provide additional protection to the power grid using only publicly available data. In particular, WISP exploits the spatio-temporal nature of the real time locational marginal prices (LMPs), in conjunction with other information such as bids, weather, outages and load data to analyze anomalous power pricing behaviors and then correlate those observations to localize regions of interest and identify potential cyber events. WISP is non-intrusive as the tool is deployed as a service in the Cloud or on premise and provides reliable information to system operators for enhanced situational awareness, without impeding energy delivery functions. The WISP technology comprises three modules: the data-driven anomaly detection core, the vulnerability and risk analysis and the root cause analysis. The data-driven anomaly detection core performs the tasks of feature selection, anomaly detection and attack region localization. The vulnerability and risk analysis module provides system level information of the vulnerable variables and times, assisting the operators in selecting monitoring and protection nodes. The root cause analysis module takes the detection results and identifies potential operational conditions that contribute to the detected anomalies. In Phase I, we have demonstrated the feasibility and effectiveness of WISP. We developed a realistic electricity market simulator capable of generating normal and attack market data under various operational conditions. We developed a series of cyber-attack detection and analysis algorithms and evaluated them under multiple data sources. Finally, we integrated all modules into an end-to-end software, providing functions for data management, data analytics and visualization. Specifically, we have achieved: (i) real-time data acceptance from external utility interfaces with >99% acceptance rate; (ii) high performance anomaly detection algorithms with >98% detection accuracy and <0.1% false alarm rate; and (iii) ultra-low computing delay <50 milliseconds. Additionally, our team developed algorithms to identify the vulnerable variables in electricity market operations and root cause analysis functions to identify major contributors to the price spikes. These ancillary modules are necessary when deploying WISP in real world industry environment. In Phase II, we have demonstrated the effectiveness of WISP software on realistic largescale power systems. We performed red team testing for the Phase I WISP software and identified software vulnerabilities and implemented corresponding mitigation solutions. We adapted the electricity market simulator for the Texas synthetic 2000-bus system and generated datasets for the false data injection attacks. We created database and visualization interfaces for the Texas system and the ISO New England system. We performed software optimization in terms of operation efficiency, computing speed and detection accuracy. Finally, we tested the software on the Texas system and the ISO New England system and evaluated the detection performance. Overall, we achieved above 89% detection rate, below 3% false alarm rate and below 37 seconds of end-to-end detection delay.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2020

K 2 CuX 3 (X = Cl, Br): All-Inorganic Lead-Free Blue Emitters with Near-Unity Photoluminescence Quantum Yield

Recently, copper(I) halides have been gaining increased attention as highly luminescent nontoxic alternatives to lead halide perovskites for optoelectronic applications. In this paper, we report preparation of blue emitting, lead free, all-inorganic halides K 2 CuX 3 (X = Cl, Br) through five synthetic methods including traditional solid-state and solution methods. The photoluminescence (PL) emission spectra of K 2 CuCl 3 and K 2 CuBr 3 exhibit narrow peaks centered at 392 and 388 nm with full widths at half-maximum (fwhm) values of ~54 nm. The visible bright blue emission is corroborated by the remarkably high photoluminescence quantum yield (PLQY) values up to ~97%. Furthermore, radioluminescence measurements on K 2 CuCl 3 yield a bright peak at 404 nm under irradiation with X-rays at 200 kVp and 20 mA, which is optimal for use with PMTs and Si photomultipliers, suggesting a strong potential of this family for radiation detection applications. Based on our combined experimental and computational investigations, the origin of the efficient luminescence in K 2 CuX 3 is attributed to the high stability self-trapped excitons (STE) formed in the one-dimensional anionic ∞ 1 [CuX 3 ] 2– chains. Advantageously, K 2 CuX 3 demonstrate improved air- and photostability compared to the previously reported copper(I) halides. The discovery of highly efficient and high stability light emitters based on earth-abundant copper(I) halides paves the way for their potential practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO 2 to Formate by Ruthenium Complexes

We show a series of 4,4'-dimethyl-2,2'-bipyridyl ruthenium complexes with carbonyl ligands were prepared and studied using a combination of electrochemical and spectroscopic methods with infrared detection to provide structural information on reaction intermediates in the photochemical reduction of CO 2 to formate in acetonitrile (CH 3 CN). An unsaturated 5-coordinate intermediate was characterized, and the hydride-transfer step to CO 2 from a singly reduced metal-hydride complex was observed with kinetic resolution. While triethanolamine (TEOA) was expected to act as a proton acceptor to ensure the sacrificial behavior of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as an electron donor, time-resolved infrared measurements revealed that about 90% of the photogenerated one-electron reduced complexes undergo unproductive back electron transfer. Furthermore, TEOA showed the ability to capture CO 2 from CH 3 CN solutions to form a zwitterionic alkylcarbonate adduct and was actively engaged in key catalytic steps such as metal-hydride formation, hydride transfer to CO 2 to form the bound formate intermediate, and dissociation of formate ion product. Collectively, the data provide an overview of the transient intermediates of Ru(II) carbonyl complexes and emphasize the importance of considering the participation of TEOA when investigating and proposing catalytic pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Detection of the large-scale tidal field with galaxy multiplet alignment in the DESI Y1 spectroscopic survey

We explore correlations between the orientations of small galaxy groups, or ‘multiplets’, and the large-scale gravitational tidal field. Using data from the Dark Energy Spectroscopic Instrument (DESI) Y1 survey, we detect the intrinsic alignment (IA) of multiplets to the galaxy-traced matter field out to separations of $100\,h^{-1}$ Mpc. Unlike traditional IA measurements of individual galaxies, this estimator is not limited by imaging of galaxy shapes and allows for direct IA detection beyond redshift $z=1$. Multiplet alignment is a form of higher order clustering, for which the scale-dependence traces the underlying tidal field and amplitude is a result of small-scale ($\lt 1h^{-1}$ Mpc) dynamics. Within samples of bright galaxies, luminous red galaxies (LRG) and emission-line galaxies, we find similar scale-dependence regardless of intrinsic luminosity or colour. This is promising for measuring tidal alignment in galaxy samples that typically display no IA. DESI’s LRG mock galaxy catalogues created from the A BACUS S UMMIT N -body simulations produce a similar alignment signal, though with a 33 per cent lower amplitude at all scales. An analytic model using a non-linear power spectrum (NLA) only matches the signal down to 20 $h^{-1}$ Mpc. Our detection demonstrates that galaxy clustering in the non-linear regime of structure formation preserves an interpretable memory of the large-scale tidal field. Multiplet alignment complements traditional two-point measurements by retaining directional information imprinted by tidal forces, and contains additional line-of-sight information compared to weak lensing. This is a more effective estimator than the alignment of individual galaxies in dense, blue, or faint galaxy samples.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Development of Lipid-Coated Semiconductor Nanosensors for Recording of Membrane Potential in Neurons

In the past decade, optical imaging methods have significantly improved our understanding of the information processing principles in the brain. Although many promising tools have been designed, sensors of membrane potential are lagging behind the rest. Semiconductor nanoparticles are an attractive alternative to classical voltage indicators, such as voltage-sensitive dyes and proteins. Such nanoparticles exhibit high sensitivity to external electric fields via the quantum-confine Stark effect. Here we report the development of semiconductor voltage-sensitive nanorods (vsNRs) that self-insert into the neuronal membrane. To facilitate interaction of the nanorods with the membrane, we functionalized their surface with the lipid mixture derived from brain extract. We describe a workflow to detect and process the photoluminescent signal of vsNRs after widefield time-lapse recordings. We also present data indicating that vsNRs are feasible for sensing membrane potential in neurons at a single-particle level. This shows the potential of vsNRs for the detection of neuronal activity with unprecedentedly high spatial and temporal resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Numerical Investigation of Fluid Flow and Space Charge in Liquid Argon Time Projection Chamber (LArTPC) Detectors

Overview This project focused on developing a high-fidelity numerical framework to simulate the multiphysics environment within Liquid Argon Time Projection Chamber (LArTPC) detectors. The primary objective was to characterize the complex interplay between ion transport, background fluid dynamics, and electric field distortions—a critical factor for the calibration and sensitivity of next-generation High Energy Physics experiments, such as DUNE. Technical Achievements The research successfully yielded a hybrid numerical space-charge solver utilizing a Cell-Centered Finite Volume Method (FVM) for ion transport coupled with a Finite Element Method (FEM) for electric potential. Key accomplishments include: • Verification & Validation: The 3-D solver was rigorously verified against 1-D analytical solutions, demonstrating high numerical accuracy in predicting space-charge-induced field deviations. • Field Distortion Analysis: 3D simulations revealed that space charge effects introduce significant non-uniformities in the electric field. Critically, the research identified that background LAr flow velocities, when comparable to ion drift velocities, markedly exacerbate these distortions. • Technology Transfer: The resulting source code and comprehensive user manuals were successfully transferred to collaborators at Fermilab, providing a portable computational tool for the broader scientific community. Challenges and Future Directions While the space-charge solver achieved all performance metrics, the integrated fluid dynamics modeling encountered convergence challenges stemming from the extreme 200-fold disparity in length scales between the detector's 37 mm inlet pipes and the 8-meter global domain. To address this, the project has identified a clear technical pivot toward Hierarchical Geometric Adaptive Mesh Refinement (HG-AMR). By implementing an h-type refinement strategy with hanging nodes, future iterations of this solver will be capable of resolving localized high-gradient inlet flows without the prohibitive computational costs of regular grids. This advancement, combined with data-driven uncertainty quantification based on MicroBooNE-style calibration, will enable the precise modeling of detector responses in large-scale cryogenic environments where direct measurement remains difficult. Impact The computational tools developed under this award provide a foundation for enhancing the energy resolution and spatial reconstruction of noble liquid detectors. By bridging the gap between theoretical fluid dynamics and experimental field calibration, this work supports the DOE’s mission to advance the frontiers of neutrino physics and dark matter detection.

42 ENGINEERING↗