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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 145 records · Page 8

TChem-atm (v2.0.0): scalable performance-portable multiphase atmospheric chemistry

We present TChem-atm, a performance-portable approach that enables efficient simulation of chemically detailed and multiphase atmospheric chemistry on modern heterogeneous computing architectures. Unlike previous efforts that rely on architecture-specific code or focus exclusively on gas-phase chemistry, TChem-atm supports fully coupled gas–aerosol systems with execution across CPUs, NVIDIA GPUs, and AMD GPUs through the Kokkos programming model. It integrates the flexible multiphase capabilities of the Community Atmospheric Model Chemistry Package (CAMP) with the high-performance kinetic routines of TChem, and includes automatic Jacobian construction with support for a range of stiff ODE solvers. In a proof-of-concept integration with the particle-resolved model PartMC, TChem-atm reproduces the existing PartMC–CAMP implementation within solver tolerances and delivers substantial GPU speedups, especially for large particle populations. Performance benchmarks reveal substantial speedups on GPU platforms, particularly for large particle populations, with consistent results across hardware backends. TChem-atm enables performance-portable execution across CPUs and GPUs, though optimal efficiency may require modest architecture-specific tuning (e.g., team and vector sizes), with up to a twofold improvement on the NVIDIA H100. It directly supports sectional and particle-resolved host models, while modal aerosol schemes require minor adaptation to provide particle-scale quantities such as representative diameters. By enabling chemically detailed, multiphase simulations with performance portability and host-model flexibility, TChem-atm facilitates the incorporation of advanced chemistry into atmospheric models.

Díaz-Ibarra, Oscar Homero [Sandia National Laborat↗

Effect of Water Chemistry on Crack Growth Rate in Neutron Irradiated X-750 and XM-19

The Advanced Test Reactor (ATR) National Science User Facility (NSUF) was used to study the effect of neutron damage on crack growth rates (CGR) under simulated boiling water reactor (BWR) water chemistry conditions using a fast neutron spectrum to accelerate the damage process. Nickel based Alloy X-750 and XM-19 were irradiated in the ATR center flux trap (CFT), with this experiment marking the first civilian project to utilize this position within the reactor. 0.4T-CT specimens were used to study crack growth rates for two sample fluences (~1.9 x 1020 n/cm2 and ~9.5 x 1020 n/cm2, E > 1MeV)) in both normal water chemistry (NWC) at 2.5 ppm O2 and hydrogen water chemistry (HWC) at ~80 ppb H2. CGR testing was conducted at a temperature of 288 °C. A decrease in CGR was observed for both alloys with the average ratio (CGR in NWC/CGR in HWC) being a factor of 281 for the XM-19 samples and a factor of 27.8 for the X-750 samples. Observed CGRs in this study showed little difference compared to non-irradiated samples (the non-irradiated XM-19 was 20% cold worked), suggesting limited sensitivity of these susceptible alloys to irradiation effects. Detailed results of CGR response to varying environmental electrochemical potential (ECP) and water purity will be presented in the context of crack growth mitigation in different water chemistries and the change in material behavior relative to non-irradiated samples of the material.

36 MATERIALS SCIENCE↗

Anion Exchange Ionomers: Impact of Chemistry on Thin-Film Properties

Ionomer thin-films (i.e., 20–100 nm) on supports serve as model systems to understand ionomer-catalyst interfacial behavior as well as the confinement-driven deviation in properties from bulk membranes. While ionomer thin-films have been examined for proton exchange ionomers, the thin-film properties of anion exchange ionomers (AEIs) remain largely unexplored. More importantly, delineating the convoluted impact of chemistry and confinement on thin-film morphology and hydration is of interest to advancing the field on functional ionic interfaces. In this work, these aspects are studied by using AEIs of different backbones (perfluorinated, aliphatic, and aromatic) and side chains (various lengths, and single versus dual functional groups). Quartz-crystal microbalance and spectroscopic ellipsometry are used to analyze density and coupled with calculated free volume fraction of thin-films to provide insights on their gas transport properties. AEI side-chain's chemical character plays a key role in how confinement modulates hydration (in thin-film versus bulk). Overall, the results elucidate the effects of backbone, side-chain chemistry versus anion/cation type in the confinement-driven changes in thin-film morphology and swelling. This study also provides new insights for tuning AEI transport functionalities at interfaces via chemistry, which can benefit the design and development of electrode-ionomers for alkaline membrane-based energy systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advancing Electrolyte Solution Chemistry and Interfacial Electrochemistry of Divalent Metal Batteries

Divalent metal (Mg, Ca, etc.) battery chemistries potentially provide a sustainable long-term technical solution for large-scale energy storage because of high natural abundance of divalent metal elements in the earth crust. Good progress has been made on materials especially electrolyte development in the past years; however, significant challenges exist, particularly the very limited fundamental understanding on electrolyte solution chemistry and interfacial electrochemistry. In this perspective, we review and discuss key discoveries and understanding of divalent battery chemistry with a focus on electrolyte-dependent interfacial electrochemistry of divalent metal anodes. A concise review of electrolyte development, operando studies of the electrified interfaces and unique charge-transfer process is provided; the knowledge gaps and future research directions are discussed.

25 ENERGY STORAGE↗

The MolSSI QCArchive project: An open-source platform to compute, organize, and share quantum chemistry data

The Molecular Sciences Software Institute's (MolSSI) Quantum Chemistry Archive (QCArchive) project is an umbrella name that covers both a central server hosted by MolSSI for community data and the Python-based software infrastructure that powers automated computation and storage of quantum chemistry (QC) results. The MolSSI-hosted central server provides the computational molecular sciences community a location to freely access tens of millions of QC computations for machine learning, methodology assessment, force-field fitting, and more through a Python interface. Facile, user-friendly mining of the centrally archived quantum chemical data also can be achieved through web applications found at the website. The software infrastructure can be used as a standalone platform to compute, structure, and distribute hundreds of millions of QC computations for individuals or groups of researchers at any scale. The QCArchiveInfrastructure is open-source (BSD-3C), code repositories can be found at github, and releases can be downloaded via PyPI and Conda. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Quantum Chemistry Data Science > Computer Algorithms and Programming

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Superatomic chemistry

Superatoms are atomic clusters with tailored size and composition that mimic the chemistry of atoms in the periodic table. However, unlike the atoms whose chemistry is governed by their valence electron orbitals, the chemistry of superatoms is governed by their highest occupied molecular orbitals. In addition, due to their large size and non-spherical geometry, superatoms can promote unusual reactions and serve as the building blocks of cluster assembled materials with properties very different from conventional materials. This perspective highlights the unique role of superatoms in chemical and material sciences by focusing on superhalogens, which not only possess electron affinities larger than those of halogens but also can be stable when multiply charged. We discuss how these unique features of superhalogens enable noble gas atoms like argon to form chemical bonds at room temperature and zinc to exhibit an oxidation state of +3. Here, the advantages of using superhalogens in the synthesis of water-resistant materials for solar cells, halogen-free electrolytes for solid-state batteries, and multiferroic materials are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent Advances in Nuclear Forensic Chemistry

Nuclear forensics is a rapidly growing field with a widespread impact on global nonproliferation. From the beginning, nuclear forensic capabilities have been inextricably bound to existing limitations within chemistry and materials science. As nuclear forensics has continued to develop as a unique field of research, new advances in chemistry have revolutionized our ability to rapidly and quantitatively analyze radioactive materials for attribution. In particular, microanalytical techniques originally developed for nanoscience, such as micro-XRF, SIMS, and SEM-EDX, have enabled spatially resolved chemical analyses to be performed with only nanograms of material. Such techniques have redefined the paradigm for pre- and postdetonation nuclear forensics, as large quantities of material are no longer necessary for full characterization and attribution. This Review explains how modern nuclear forensic techniques have developed from their origins in chemistry and provides real-world examples of how these techniques have been used to characterize radioactive materials, including fallout from nuclear detonations such as the 1945 Trinity test.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Evaluating the evidence for exponential quantum advantage in ground-state quantum chemistry

Due to intense interest in the potential applications of quantum computing, it is critical to understand the basis for potential exponential quantum advantage in quantum chemistry. Here we gather the evidence for this case in the most common task in quantum chemistry, namely, ground-state energy estimation, for generic chemical problems where heuristic quantum state preparation might be assumed to be efficient. The availability of exponential quantum advantage then centers on whether features of the physical problem that enable efficient heuristic quantum state preparation also enable efficient solution by classical heuristics. Through numerical studies of quantum state preparation and empirical complexity analysis (including the error scaling) of classical heuristics, in both ab initio and model Hamiltonian settings, we conclude that evidence for such an exponential advantage across chemical space has yet to be found. While quantum computers may still prove useful for ground-state quantum chemistry through polynomial speedups, it may be prudent to assume exponential speedups are not generically available for this problem.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Significant stream chemistry response to temperature variations in a high-elevation mountain watershed

Abstract High-elevation mountain regions, central to global freshwater supply, are experiencing more rapid warming than low-elevation locations. High-elevation streams are therefore potentially critical indicators for earth system and water chemistry response to warming. Here we present concerted hydroclimatic and biogeochemical data from Coal Creek, Colorado in the central Rocky Mountains at elevations of 2700 to 3700 m, where air temperatures have increased by about 2 °C since 1980. We analyzed water chemistry every other day from 2016 to 2019. Water chemistry data indicate distinct responses of different solutes to inter-annual hydroclimatic variations. Specifically, the concentrations of solutes from rock weathering are stable inter-annually. Solutes that are active in soils, including dissolved organic carbon, vary dramatically, with double to triple peak concentrations occurring during snowmelt and in warm years. We advocate for consistent and persistent monitoring of high elevation streams to record early glimpse of earth surface response to warming.

54 ENVIRONMENTAL SCIENCES↗

Role of nanoparticle size and surface chemistry on ion transport and nanostructure of perfluorosulfonic acid ionomer nanocomposites

In this work, we present a systematic investigation of the impact of silica nanoparticle (SiNP) size and surface chemistry on the nanoparticle dispersion state and the resulting morphology and vanadium ion permeability of the composite ionomer membranes. Specifically, Nafion containing a mass fraction of 5% silica particles, ranging in nominal diameters from 10 nm to >1 μm and with both sulfonic acid- and amine-functionalized surfaces, was fabricated. Most notably, an 80% reduction in vanadium ion permeability was observed for ionomer membranes containing amine-functionalized SiNPs at a nominal diameter of 200 nm. Further, these membranes exhibited an almost 400% increase in proton selectivity when compared to pristine Nafion. Trends in vanadium ion permeability within a particular nominal diameter were seen to be a function of the surface chemistry, where, for example, vanadyl ion permeability was observed to increase with increasing particle size for membranes containing unfunctionalized SiNPs, while it was seen to remain relatively constant for membranes containing amine-functionalized SiNPs. In general, the silica particles tended to exhibit a higher extent of aggregation as the size of the particles was increased. From small-angle neutron scattering experiments, an increase in the spacing of the hydrophobic domains was observed for all composite membranes, though particle size and surface chemistry were seen to have varying impacts on the spacing of the ionic domains of the ionomer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Circularity in polymers: addressing performance and sustainability challenges using dynamic covalent chemistries

The circularity of current and future polymeric materials is a major focus of fundamental and applied research, as undesirable end-of-life outcomes and waste accumulation are global problems that impact our society. The recycling or repurposing of thermoplastics and thermosets is an attractive solution to these issues, yet both options are encumbered by poor property retention upon reuse, along with heterogeneities in common waste streams that limit property optimization. Dynamic covalent chemistry, when applied to polymeric materials, enables the targeted design of reversible bonds that can be tailored to specific reprocessing conditions to help address conventional recycling challenges. In this review, we highlight the key features of several dynamic covalent chemistries that can promote closed-loop recyclability and we discuss recent synthetic progress towards incorporating these chemistries into new polymers and existing commodity plastics. Next, we outline how dynamic covalent bonds and polymer network structure influence thermomechanical properties related to application and recyclability, with a focus on predictive physical models that describe network rearrangement. Finally, we examine the potential economic and environmental impacts of dynamic covalent polymeric materials in closed-loop processing using elements derived from techno-economic analysis and life-cycle assessment, including minimum selling prices and greenhouse gas emissions. Throughout each section, we discuss interdisciplinary obstacles that hinder the widespread adoption of dynamic polymers and present opportunities and new directions toward the realization of circularity in polymeric materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The inorganic chemist's guide to actinide radiation chemistry: a review

This review aims to provide an overview of the current state of radiation chemistry with respect to the actinide elements, thorium through californium. Despite the inherent radioactivity of the actinides, only a few studies explore the effects of ionizing radiation on their redox chemistry and surrounding environment. This fundamental knowledge gap, coupled with the current renaissance in actinide-based technologies such as nuclear power, space exploration, and medicine, underscores the importance of research in this interdisciplinary area. This review will focus on the interactions between reactive species formed by radiolysis with actinides and their complexes, offering an inorganic chemist's perspective on research in radiation chemistry. In addition, a thorough discussion of our current understanding of radiation-induced changes in actinide speciation in both aqueous solution and the solid-state will be provided, focusing on changes in oxidation state distribution, complexation, and secondary coordination effects within inorganic materials. Finally, this review will discuss challenges and opportunities for inorganic chemists to explore this unique intersection of fields.

Actinides↗

Design principles of heterointerfacial redox chemistry for highly reversible lithium metal anode

High electrochemical reversibility is required for the application of high-energy-density lithium (Li) metal batteries; however, inactive Li formation and SEI (solid electrolyte interface)-instability-induced electrolyte consumption cause low Coulombic efficiency (CE). The prior interfacial chemical designs in terms of alloying kinetics have been used to enhance the CE of Li metal anode; however, the role of its redox chemistry at heterointerfaces remains a mystery. Herein, the relationship between heterointerfacial redox chemistry and electrochemical transformation reversibility is investigated. It is demonstrated that the lower redox potential at heterointerface contributes to higher CE, and this enhancement in CE is primarily due to the regulation of redox chemistry to Li deposition behavior rather than the formation of SEI films. Low oxidation potential facilitates the formation of the surface with the highly electrochemical binding feature after Li stripping, and low reduction potential can maintain binding ability well during subsequent Li plating, both of which homogenize Li deposition and thus optimize CE. In particular, Mg hetero-metal with ultra-low redox potential enables Li metal anode with significantly improved CE (99.6%) and stable cycle life for 700 cycles at 3.0 mA cm -2 . This work provides insight into the heterointerfacial design principle of next-generation negative electrodes for highly reversible metal batteries.

25 ENERGY STORAGE↗

Sustainable chemistry with plasmonic photocatalysts

There is a pressing global need to increase the use of renewable energy sources and limit greenhouse gas emissions. Towards this goal, highly efficient and molecularly selective chemical processes that operate under mild conditions are critical. Plasmonic photocatalysis uses optically resonant metallic nanoparticles and their resulting plasmonic, electronic, and phononic light-matter interactions to drive chemical reactions. The promise of simultaneous high-efficiency and product-selective reactions with plasmon photocatalysis provides a compelling opportunity to rethink how chemistry is achieved. Plasmonic nanoparticles serve as nanoscale ‘antennas’ that enable strong light–matter interactions, surpassing the light-harvesting capabilities one would expect purely from their size. Complex composite structures, combining engineered light harvesters with more chemically active components, are a focal point of current research endeavors. In this review, we provide an overview of recent advances in plasmonic catalysis. We start with a discussion of the relevant mechanisms in photochemical transformations and explain hot-carrier generation and distributions from several ubiquitous plasmonic antennae. Then we highlight three important types of catalytic processes for sustainable chemistry: ammonia synthesis, hydrogen production and CO 2 reduction. To help elucidate the reaction mechanism, both state-of-art electromagnetic calculations and quantum mechanistic calculations are discussed. This review provides insights to better understand the mechanism of plasmonic photocatalysis with a variety of metallic and composite nanostructures toward designing and controlling improved platforms for green chemistry in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Data and Scripts associated with “Lambda-PFLOTRAN: Workflow for Incorporating Organic Matter Chemistry Informed by Ultra High Resolution Mass Spectrometry into Biogeochemical Modeling.”

This data package is associated with the publication “Lambda-PFLOTRAN: Workflow for Incorporating Organic Matter Chemistry Informed by Ultra High Resolution Mass Spectrometry into Biogeochemical Modeling” submitted to Geoscientific Model Development (Muller et al., 2024). In this manuscript, organic matter chemistry and thermodynamics are directly connected to reactive transport simulators through the newly developed Lambda-PFLOTRAN (Parallel Reactive Flow and Transport model) workflow tool that succinctly incorporates organic matter chemistry data generated from Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) into reaction networks to simulate aerobic respiration of the organic matter and the resulting biogeochemistry. Lambda-PFLOTRAN is a python-based workflow, executed through a Jupyter Notebook interface, that digests raw FTICR-MS data, develops a representative reaction network based on substrate-explicit thermodynamic modeling (also termed lambda modeling due to its key thermodynamic parameter λ used therein), and completes a biogeochemical simulation with the open source, reactive flow, and transport code PFLOTRAN. This data package contains Jupyter Notebook based workflows for two test cases for running biogeochemical simulations of organic matter oxidation identified by FTICR-MS. It contains four primary folders (workflow, data, src, and analysis), a file-level metadata file (Muller_2024_Lambda_PFLOTRAN_Manuscript_Data_Package_flmd.csv) that lists all the files contained in this data package with a short description of each, and a data dictionary (Muller_2024_Lambda_PFLOTRAN_Manuscript_Data_Package_dd.csv) file that describes the tabular column headers. The ‘workflow’ folder contains the Jupyter Notebook based workflows for running the lambda analysis, PFLOTRAN simulation, sensitivity analysis and parameter estimation. The ‘data’ folder contains the FTICR-MS data, initial conditions, and incubation data for test cases 1 and 2 in folders titled ‘WHONDRS’ and ‘Colloids’, respectively. The data folder also has a ‘Database’ folder containing a reaction network for bulk organic matter (assumed to be CH2O) and a general database for PFLOTRAN (hanford_rxn_network). The CH2O reaction network defines bulk organic matter oxidation. Biogeochemical simulations are completed for both the lambda binned organic matter and bulk organic matter reaction networks. The ‘hanford_rxn_network’ database includes information required for PFLTORAN simulations including ion size, molar mass, and charge of the aqueous species, gases, and minerals phases. The ‘src’ folder contains python source codes for performing lambda analysis, PFLOTRAN simulation, sensitivity analysis and parameter estimation. The ‘analysis’ folder contains outputs from the test cases 1 and 2 including lambda analysis, PFLOTRAN runs and the calibration results.

54 ENVIRONMENTAL SCIENCES↗

Chemically Stable Styrenic Electrospun Membranes with Tailorable Surface Chemistry

Membranes with tailorable surface chemistry have applications in a wide range of industries. Synthesizing membranes from poly(chloromethyl styrene) directly incorporates an alkyl halide surface-bound initiator which can be used to install functional groups via SN2 chemistry or graft polymerization techniques. In this work, poly(chloromethyl styrene) membranes were synthesized through electrospinning. After fabrication, membranes were crosslinked with a diamine, and the chemical resistance of the membranes was evaluated by exposure to 10 M nitric acid, ethanol, or tetrahydrofuran for 24 h. The resulting membranes had diameters on the order of 2–5 microns, porosities of >80%, and permeance on the order of 10,000 L/m2/h/bar. Crosslinking the membranes generally increased the chemical stability. The degree of crosslinking was approximated using elemental analysis for nitrogen and ranged from 0.5 to 0.9 N%. The poly(chloromethyl styrene) membrane with the highest degree of crosslinking did not dissolve in THF after 24 h and retained its high permeance after solvent exposure. The presented chemically resistant membranes can serve as a platform technology due to their versatile surface chemistry and can be used in membrane manufacturing techniques that require the membrane to be contacted with organic solvents or monomers. They can also serve as a platform for separations that are performed in strong acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Irreparable Interphase Chemistry Degradation Induced by Temperature Pulse in Lithium–Ion Batteries

While it is widely recognized that the operating temperature significantly affects the energy density and cycle life of lithium-ion batteries, the consequence of electrode-electrolyte interphase chemistry to sudden environmental temperature changes remains inadequately understood. Here, we systematically investigate the effects of a temperature pulse (T pulse) on the electrochemical performance of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) pouch full cells. By utilizing advanced characterization tools, such as time-of-flight secondary-ion mass spectrometry, we reveal that the T pulse can lead to an irreversible degradation of cathode-electrolyte interphase chemistry and architecture. Despite negligible immediate impacts on the solid-electrolyte interphase (SEI) on graphite anode, aggregated cathode-to-anode chemical crossover gradually degrades the SEI by catalyzing electrolyte reduction decomposition and inducing metallic dead Li formation because of insufficient cathode passivation after the T pulse. Consequently, pouch cells subjected to the T pulse show an inferior cycle stability to those free of the T pulse. Furthermore, this work unveils the effects of sudden temperature changes on the interphase chemistry and cell performance, emphasizing the importance of a proper temperature management in assessing performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fragme∩t: An Open‐Source Framework for Multiscale Quantum Chemistry Based on Fragmentation

Fragment-based quantum chemistry offers a means to circumvent the nonlinear computational scaling of conventional electronic structure calculations, by partitioning a large calculation into smaller subsystems then considering the many-body interactions between them. Variants of this approach have been used to parameterize classical force fields and machine learning potentials, applications that benefit from interoperability between quantum chemistry codes. However, there is a dearth of software that provides interoperability yet is purpose-built to handle the combinatorial complexity of fragment-based calculations. To fill this void we introduce “Fragme∩t”, an open-source software application that provides a tool for community validation of fragment-based methods, a platform for developing new approximations, and a framework for analyzing many-body interactions. Fragme∩t includes algorithms for automatic fragment generation and structure modification, and for distance- and energy-based screening of the requisite subsystems. Checkpointing, database management, and parallelization are handled internally and results are archived in a portable database. Interfaces to various quantum chemistry engines are easy to write and exist already for Q-Chem, PySCF, xTB, Orca, CP2K, MRCC, Psi4, NWChem, GAMESS, and MOPAC. Applications reported here demonstrate parallel efficiencies around 96% on more than 1000 processors but also showcase that the code can handle large-scale protein fragmentation using only workstation hardware, all with a codebase that is designed to be usable by non-experts. Fragme∩t conforms to modern software engineering best practices and is built upon well established technologies including Python, SQLite, and Ray. The source code is available under the Apache 2.0 license.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗