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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Determining Activity Coefficients of SOA from Isothermal Evaporation in a Laboratory Chamber

Nonideal molecular interactions in aerosol particles influence the partitioning of semivolatile organic compounds (SVOCs). However, few direct measurements exist that determine activity coefficients (γ), which quantify nonideality, for individual organic compounds in different atmospheric mixtures. By measuring the isothermal evaporation of SOA formed from multifunctional SVOCs in an environmental chamber, this study determines the mole-fraction-based γ of the bulk SOA in a variety of pre-existing chemically complex particles, approximated as if the bulk SOA behaved like a single SVOC. These multicomponent mixtures contain molecular structures commonly found in the atmosphere. When treated as a single liquid phase, γ of the bulk SOA tends to increase from ~1 to ~5 as the organic seeds and the SOA have more differing polarities. A high computed γ value of 74 for a wet ammonium sulfate-SOA system indicates phase separation. The γ for some individual species was also quantified based on gas-phase measurements and AIOMFAC model predictions. However, the bulk SOA γ cannot be explained by the simplified speciated SVOC–seed interactions, suggesting incomplete compositional understanding of the bulk SOA. In this work, these results demonstrate a method to quantify nonideal behavior and show that it can occur in multicomponent mixtures and therefore influence OA formation, evolution, and lifetimes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Programmable simulations of molecules and materials with reconfigurable quantum processors

Simulations of quantum chemistry and quantum materials are believed to be among the most important applications of quantum information processors. However, realizing practical quantum advantage for such problems is challenging because of the prohibitive computational cost of programming typical problems into quantum hardware. Here we introduce a simulation framework for strongly correlated quantum systems represented by model spin Hamiltonians that uses reconfigurable qubit architectures to simulate real-time dynamics in a programmable way. Our approach also introduces an algorithm for extracting chemically relevant spectral properties via classical co-processing of quantum measurement results. We develop a digital–analogue simulation toolbox for efficient Hamiltonian time evolution using digital Floquet engineering and hardware-optimized multi-qubit operations to accurately realize complex spin–spin interactions. As an example, we propose an implementation based on Rydberg atom arrays. In addition, we show how detailed spectral information can be extracted from the dynamics through snapshot measurements and single-ancilla control, enabling the evaluation of excitation energies and finite-temperature susceptibilities from a single dataset. To illustrate the approach, we show how to use the method to compute key properties of a polynuclear transition-metal catalyst and two-dimensional magnetic materials.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Solvation directed morphological control in metal oxide nanostructures

The development of structural hierarchy on various length scales during the crystallization process is ubiquitous in biological systems and minerals and is common in synthetic nanomaterials. The driving forces for the formation of complex architectures range from local interfacial interactions, that modify interfacial speciation, local supersaturation, and nucleation barriers, to macroscopic interparticle forces. Although it is enticing to interpret the formation of hierarchical architectures as the assembly of independently nucleated building blocks, crystallization pathways often follow monomer-by-monomer addition with structural complexity arising from interfacial chemical coupling and strongly correlated fluctuation dynamics in the electric double layers. Here, we show that the development of structural hierarchy through heterogeneous nucleation is driven by dipolar and solvation forces. Specifically, coupled simulations and experimental studies revealed that dipole build-up along the slow growth direction can trigger twinning and the development of branched architectures. Enthalpic solvation interactions were shown to either enhance or reduce the dipole moment of the nanoparticles and, thereby, control crystal morphology and architecture. The systematic studies of chemical coupling between different solvents and undercoordinated surface atoms of the growing nanocrystals revealed the mechanism of dimensionality control and the development of structural hierarchy without ligands or structure-directing agents.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Evaluation of 6-OxP-CD, an Oxime-based cyclodextrin as a viable medical countermeasure against nerve agent poisoning: Experimental and molecular dynamic simulation studies on its inclusion complexes with cyclosarin, soman and VX

The ability of the cyclodextrin-oxime construct 6-OxP-CD to bind and degrade the nerve agents Cyclosarin (GF), Soman (GD) and S -[2-[Di(propan-2-yl)amino]ethyl] O -ethyl methylphosphonothioate (VX) has been studied using 31 P-nuclear magnetic resonance (NMR) under physiological conditions. While 6-OxP-CD was found to degrade GF instantaneously under these conditions, it was found to form an inclusion complex with GD and significantly improve its degradation (t 1/2 ~ 2 hrs) relative over background (t 1/2 ~ 22 hrs). Consequently, effective formation of the 6-OxP-CD:GD inclusion complex results in the immediate neutralization of GD and thus preventing it from inhibiting its biological target. In contrast, NMR experiments did not find evidence for an inclusion complex between 6-OxP-CD and VX, and the agent’s degradation profile was identical to that of background degradation (t 1/2 ~ 24 hrs). As a complement to this experimental work, molecular dynamics (MD) simulations coupled with Molecular Mechanics-Generalized Born Surface Area (MM-GBSA) calculations have been applied to the study of inclusion complexes between 6-OxP-CD and the three nerve agents. These studies provide data that informs the understanding of the different degradative interactions exhibited by 6-OxP-CD with each nerve agent as it is introduced in the CD cavity in two different orientations (up and down). For its complex with GF, it was found that the oxime in 6-OxP-CD lies in very close proximity (P GF …O Oxime ~ 4–5 Å) to the phosphorus center of GF in the ‘down GF ’ orientation for most of the simulation accurately describing the ability of 6-OxP-CD to degrade this nerve agent rapidly and efficiently. Further computational studies involving the center of masses (COMs) for both components (GF and 6-OxP-CD) also provided some insight on the nature of this inclusion complex. Distances between the COMs (ΔCOM) lie closer in space in the ‘down GF ’ orientation than in the ‘up GF ’ orientation; a correlation that seems to hold true not only for GF but also for its congener, GD. In the case of GD, calculations for the ‘down GD ’ orientation showed that the oxime functional group in 6-OxP-CD although lying in close proximity (P GD …O Oxime ~ 4–5 Å) to the phosphorus center of the nerve agent for most of the simulation, adopts another stable conformation that increase this distance to ~ 12–14 Å, thus explaining the ability of 6-OxP-CD to bind and degrade GD but with less efficiency as observed experimentally (t 1/2 ~ 4 hr. vs. immediate). Lastly, studies on the VX:6-OxP-CD system demonstrated that VX does not form a stable inclusion complex with the oxime-bearing cyclodextrin and as such does not interact in a way that is conducive to an accelerated degradation scenario. Collectively, these studies serve as a basic platform from which the development of new cyclodextrin scaffolds based on 6-OxP-CD can be designed in the development of medical countermeasures against these highly toxic chemical warfare agents.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Fundamental limitations on photoisomerization from thermodynamic resource theories

Small, out-of-equilibrium, and quantum systems defy simple thermodynamic expressions. Such systems are exemplified by molecular switches, which exchange heat with a bath. These molecules can photoisomerize, or change conformation, or switch, on absorbing light. The photoisomerization probability depends on kinetic details that couple the molecule’s energetics to its dissipation. Therefore, a simple, general, thermodynamic-style bound on the photoisomerization probability seems out of reach. We derive such a bound using a resource theory. The resource-theory framework is a set of mathematical tools, developed in quantum information theory, used to generalize thermodynamics to small and quantum settings. From this toolkit has been derived a generalization of the second law, the thermomajorization preorder. We use thermomajorization to upper-bound the photoisomerization probability. Then, we compare the bound with an equilibrium prediction and with a Lindbladian model. We identify a realistic parameter regime in which the Lindbladian evolution saturates the thermomajorization bound. We also quantify the energy coherence in the electronic degree of freedom, and we argue that this coherence cannot promote photoisomerization. Overall, this work illustrates how quantum-information-theoretic thermodynamics can elucidate complex quantum processes in nature, experiments, and synthetics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Complex surface topographic changes from explosive experiments at the Dry Alluvium Geology site, southern Nevada, United States

Understanding the surface topographic change that results from underground explosions is important for global security. Current techniques to relate the surface change to underground explosion characteristics usually involve assuming the earth has homogenous properties, leading to highly variable interpretations. Here we use an unoccupied aerial platform and a digital single lens reflex camera along with 200+ ground control points surveyed with a real-time kinematic global navigation satellite system to measure the surface topographic change resulting from two underground explosions at the Dry Alluvium Geology site in Yucca Flat, Nevada National Security Site, southern Nevada, United States. We find areas of 5–7 cm of subsidence that are not directly above the explosion source but rather 200–300 m away. For experiment DAG2, this zone is located south and west of the explosion, while for DAG4, there is a zone of subsidence located northeast of the explosion. In addition, late-time measurements show as much as 5 cm of horizontal change without measurable associated vertical change in the weeks following DAG4 but not DAG2. These indicate that the deformation resulting from underground chemical explosions can be very complex and bear little to no resemblance to predictions using half-space models. It is likely the tectonic environment plays a significant role in controlling the surface change, but the details are not fully understood.

58 GEOSCIENCES↗
DOE OSTI2021

Nanoparticle/Polyelectrolyte Complexes for Biomimetic Constructs

Abstract Constructing all‐aqueous systems with tailored geometries can generate a new class of biomimetic materials, a fascinating but challenging goal to achieve. Here, by taking advantage of the interfacial complexation of a polyelectrolyte (PE) and cellulose nanocrystals (CNCs), a unique interfacial PE/CNC complex is demonstrated for the stabilization of aqueous two‐phase systems and for the fabrication of all‐aqueous double emulsions and 3D constructs. The thickness of PE/CNC complex can be effectively adjusted by tuning the osmotic stress imbalance between the two aqueous phases and, during the formation and thickening of PE/CNC complex, individual assemblies can be connected to design hierarchical all‐aqueous structures. This new platform affords tremendous potential for engineering biomimetic constructs with advanced functionality, that can be used for chemical separation, delivery, and biphasic cascading reaction vessels.

Yin, Yixuan↗
DOE OSTI2025

Plastic from CO 2 , Water, and Electricity: Tandem Electrochemical CO 2 Reduction and Thermochemical Ethylene-CO Copolymerization

Converting CO 2 into industrially useful products is an appealing strategy for utilization of an abundant chemical resource. Electrochemical CO 2 reduction (eCO 2 R) offers a pathway to convert CO 2 into CO and ethylene, using renewable electricity. Here, these products can be efficiently copolymerized by organometallic catalysts to generate polyketones. However, the conditions for these reactions are very different, presenting the challenge of coupling microenvironments typically encountered for the transformation of CO 2 into highly complex but desirable multicarbon products. Herein, we present a system to produce polyketone plastics entirely derived from CO 2 and water, where both the CO and C 2 H 4 intermediates are produced by eCO 2 R. In this system, a combination of Cu and Ag gas diffusion electrodes is used to generate a gas mixture with nearly equal concentrations of CO and C 2 H 4 , and a recirculatory CO 2 reduction loop is used to reach concentrations of above 11% each, leading to a current-to-polymer efficiency of up to 51% and CO 2 utilization of 14%.

carbon storage↗
DOE OSTI2024

Improving the reliability of machine learned potentials for modeling inhomogeneous liquids

The atomic-scale response of inhomogeneous fluids at interfaces and surrounding solute particles plays a critical role in governing chemical, electrochemical, and biological processes. Classical molecular dynamics simulations have been applied extensively to simulate the response of fluids to inhomogeneities directly, but are limited by the accuracy of the underlying interatomic potentials. Here, we use neural network potentials (NNPs) trained to ab initio simulations to accurately predict the inhomogeneous responses of two distinct fluids: liquid water and molten NaCl. Although NNPs can be readily trained to model complex bulk systems across a range of state points, we show that to appropriately model a fluid's response at an interface, relevant inhomogeneous configurations must be included in the training data. In order to sufficiently sample appropriate configurations of such inhomogeneous fluids, we develop protocols based on molecular dynamics simulations in the presence of external potentials. We demonstrate that NNPs trained on inhomogeneous fluid configurations can more accurately predict several key properties of fluids—including the density response, surface tension and size-dependent cavitation free energies—for liquid water and molten NaCl, compared to both empirical interatomic potentials and NNPs that are not trained on such inhomogeneous configurations. This work therefore provides a first demonstration and framework to extract the response of inhomogeneous fluids from first principles for classical density-functional treatment of fluids free from empirical potentials.

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

Photodriven electron-transfer dynamics in a series of heteroleptic Cu(I)–anthraquinone dyads

Solar fuels catalysis is a promising route to efficiently harvesting, storing, and utilizing abundant solar energy. To achieve this promise, however, molecular systems must be designed with sustainable components that can balance numerous photophysical and chemical processes. To that end, here we report on the structural and photophysical characterization of a series of Cu(I)–anthraquinone-based electron donor–acceptor dyads. The dyads utilized a heteroleptic Cu(I) bis-diimine architecture with a copper(I) bis-phenanthroline chromophore donor and anthraquinone electron acceptor. We characterized the structures of the complexes using x-ray crystallography and density functional theory calculations and the photophysical properties via resonance Raman and optical transient absorption spectroscopy. The calculations and resonance Raman spectroscopy revealed that excitation of the Cu(I) metal-to-ligand charge-transfer (MLCT) transition transfers the electron to a delocalized ligand orbital. The optical transient absorption spectroscopy demonstrated that each dyad formed the oxidized copper–reduced anthraquinone charge-separated state. Unlike most Cu(I) bis-phenanthroline complexes where increasingly bulky substituents on the phenanthroline ligands lead to longer MLCT excited-state lifetimes, here, we observe a decrease in the long-lived charge-separated state lifetime with increasing steric bulk. The charge-separated state lifetimes were best explained in the context of electron-transfer theory rather than with the energy gap law, which is typical for MLCT excited states, despite the complete conjugation between the phenanthroline and anthraquinone moieties.

14 SOLAR ENERGY↗
DOE OSTI2024

Summary Report on Ion Irradiation Study of Ceramic Coating on Suppressing FCCI

Advanced cladding is critical for advanced nuclear reactors with an enhanced performance in radiation tolerance and neutron transparency. Using advanced cladding will ensure the adequate thermal conductivity and mechanical stability of the cladding base material, corrosion resistance, high-temperature coolant compatibility of the cladding surface, and chemical stability in the cladding inner wall against fuel cladding chemical interaction (FCCI). An innovative cladding with a three-layer structure (i.e., a modified surface, a clad base material, and a modified inner wall) promises to meet all these requirements. Initial research and development (R&D) regarding this innovative cladding seek to demonstrate the effectiveness of a thin ceramic coating in suppressing FCCI under ion irradiation to high dose. This United States (U.S.) Department of Energy (DOE)–Office of Nuclear Energy (NE) project report summarizes the results of recent ion irradiation studies of diffusion-couple samples with details of an ion irradiation experiment, the characterization of the interface microstructure of cerium (Ce)/titanium nitride (TiN)/oxide-dispersion strengthened (ODS), Ce/TiN/iron (Fe), Ce/ODS, and Ce/Fe samples irradiated with 80 million electron-volts (MeV) of xenon (Xe) ions to 100 displacements per atom (dpa) at 500?C using the Argonne Tandem Linac Accelerator System (ATLAS) facility at Argonne National Laboratory (ANL). The results of the ODS-substrate sample are encouraging and demonstrate the effectiveness of a thin ceramic coating on FCCI mitigation under irradiation. The results from an Fe-substrate sample revealed a complex microstructure, and the root cause is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Probing complex geophysical geometries with chattering dust

Abstract The modern energy economy and environmental infrastructure rely on the flow of fluids through fractures in rock. Yet this flow cannot be imaged directly because rocks are opaque to most probes. Here we apply chattering dust, or chemically reactive grains of sucrose containing pockets of pressurized carbon dioxide, to study rock fractures. As a dust grain dissolves, the pockets burst and emit acoustic signals that are detected by distributed sets of external ultrasonic sensors that track the dust movement through fracture systems. The dust particles travel through locally varying fracture apertures with varying speeds and provide information about internal fracture geometry, flow paths and bottlenecks. Chattering dust particles have an advantage over chemical sensors because they do not need to be collected, and over passive tracers because the chattering dust delineates the transport path. The current laboratory work has potential to scale up to near-borehole applications in the field.

58 GEOSCIENCES↗
DOE OSTI2022

An approach to nearest neighbor analysis of pigment-protein complexes using chemical cross-linking in combination with mass spectrometry

Herein, protein cross-linking is the process of chemically joining two amino acids in a protein or protein complex by a covalent bond. When combined with mass spectrometry, it becomes one of the structural mass spectrometry techniques gaining in importance for deriving valuable three-dimensional structural information on proteins and protein complexes. This platform complements existing structural methods, such as NMR spectroscopy, X-ray crystallography, and cryo-EM. Photosynthetic pigment protein complexes serve as light-energy harvesting systems and perform photochemical conversion as part of the “early events” of photosynthesis. This chapter outlines how to prepare cross-linking pigment protein complex samples for LC-MS/MS analysis, including identification of the cross-linked species, network analysis in a protein complex, and structural modeling and justification.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Structural and chemical disorder enhance point defect diffusion and atomic transport in Ni 3 Al-based γ' phase

The ordered L1 2 γ' Ni 3 Al intermetallic inclusions are routinely used as strengthening constituents in Ni-based superalloys and recent high-entropy alloys. As there are different metallic elements relative to the alloy matrix, the composition of γ' phase inclusions usually suffers some variations. In this work, we studied the elemental partition and its influence on atomic transport properties in a model (NiCo) 3 Al γ' phase with chemical and structural disorder. Combining the Monte Carlo and molecular static techniques, we first determined the elemental distribution in such compositionally-complexed γ' phase. The results suggest that Co tends to segregate, which profoundly influences defect energetics and diffusion properties. By modeling thermally activated diffusion by molecular dynamics, we found that chemical disorder induced by Co can enhance vacancy diffusion while significantly suppress diffusion via interstitial atom migration, as compared to the stoichiometric γ' Ni 3 Al. We further reveal that these observations are closely related to the defect energetics in these systems. Furthermore, our results explain the effects of disorder, long- and short-range orders on the diffusion properties in multicomponent intermetallic alloys, which helps to understand the stability and, thus, γ'-phase-assisted strengthening at different conditions including annealing and irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hydro-chemo-mechanical phase field formulation for corrosion induced cracking in reinforced concrete

Steel corrosion induced cracking in reinforced concrete structures is often caused by volumetric straining at the steel-concrete interface. This volumetric strain is mainly controlled by the rate of generation of corrosion product, which depends on the diffusion of Cl{sup −} and dissolved O{sub 2} as well as the chemical reaction at the steel-concrete interface. While many numerical modeling techniques have been proposed to tackle this complex phenomenon, most have been limited to using staggered solution schemes, where the diffusion, chemical reaction, mechanical strain, and crack fields are solved for separately. Unfortunately, such approaches introduce numerical errors that can lead to unrealistic predictions. Therefore, a coupled solution, is needed to remove the formulation induced errors and understand this complex phenomenon. To provide a unifying solution framework for corrosion induced cracking in reinforced concrete, a phase field formulation is presented and implemented with FEM algorithms. The governing equations are derived from the system's free energy and Fick's law of diffusion. The proposed formulation was first validated in 1D by comparing the modeling results with the semi-analytical solution approximated via Laurent series to avoid singularities in the complex domain. 2D plane strain solutions to the embedded rebar undergoing corrosion induced cracking with pre-cracks are also presented and compared with the approximated solutions from linear elastic fracture mechanics theory (LEFM). The modeling of crack propagation enabled by the proposed formulation is also presented along with parametric studies to reveal the roles of the fracture toughness and permeability of the concrete on the corrosion induced cracking. A case study was also conducted on H-pile steel with concrete jackets to demonstrate the feasibility of modeling corrosion induced fracture in reinforced concrete structures with complex steel-concrete interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Comparison of semi-doped PANI/DBSA complex achieved by thermal doping and roll-mill process: A new perspective for application

Conductive polymers have garnered extensive attention over the last few decades owing to their vast applications and relative ease of production. One such polymer is PANI; with versatile thermo-mechanical, chemical, and electrical properties, has been researched for varied applications in the field of electronics, electrodes and corrosion protection. In this study, we focus on an alternative route to process semi-doped PANI/DBSA complexes with special focus on material properties for improved processability. This study investigates the influence of two different material preparation techniques: roll-milling and thermal-doping, on the formability and processability of such polymer-complex systems. Results confirm similar doping levels achieved in both processes and shear-thinning behavior was only observed for roll-milled samples. These results underline the formability of roll-milled PANI/DBSA with thermosetting resins. It essentially explains the production route and offers a perspective for commercial manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mechanistic Studies of an Iron-Catalyzed Intermolecular C–H Amination Reaction under Catalytic Conditions and Having a Large KIE

The conversion of C–H bonds into amines by nitrene insertion is an attractive transformation since it is both atom- and step-economical, and provides a direct route to functionalizing hydrocarbons. Using an iron catalyst [{( tBu pyrr) 2 pyr}Fe(OEt 2 )] (1-OEt 2 ) (( tBu pyrr) 2 pyr 2– = 3,5- t Bu 2 -bis(pyrrolyl)pyridine), we recently demonstrated the catalytic conversion of weak C–H bonds into secondary amines using aryl azides as the nitrene source [Zars, E.; Angew. Chem., Int. Ed. 2023, 62, e202311749]. Here, we describe detailed mechanistic studies of this intermolecular C–H amination reaction under catalytic conditions. We find by Variable Time Normalization Analysis (VTNA) that the conversion of xanthene (2-H 2 ) and 2,4,6-trimethyl-phenyl azide ( Me 3) catalyzed by 1-OEt 2 is an overall 3/2 order process, being 1 st order in 2-H 2 and half order in Me 3. A kinetic isotope effect study (KIE) using 2-d 2 results in a significant decrease in the rate (KIE = 61(15)), which clearly implicates the C–H insertion step as rate-determining. Furthermore, treatment of 1-OEt 2 with one equivalent of N 3 -2,6- i Pr 2 –C 6 H 3 yields the mixed-valence C–N coupled product [( tBu pyrr) 2 pyrFe-N═C(2,6 i Pr 2 –Ph)═N-(2,6 i Pr 2 –Ph))Fe tBu pyrrpyr(2-H-pyrr)] (5 iPr ). Quantum chemical calculations confirm the electronic structure of the mixed-valence dimer in 5 iPr and rationalize the Hammett correlation by a delicate balance in the dinuclearization of the catalytically active monomers. Calculations further indicate significant tunneling for the pivotal H atom abstraction by the iron-imidyl complex. Combining all these results allows us to propose a mechanism consisting of imido formation in equilibrium with a radical-coupled diiron system, followed by stepwise C–H insertion via a linear H atom abstraction transition state and subsequent radical rebound.

azides↗