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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy

Theoretical descriptors differentiate the catalytic activity of materials for the oxygen evolution reaction by the strength of oxygen binding in the reactive intermediate created upon electron transfer. Recently, time-resolved spectroscopy of a photo-electrochemically driven oxygen evolution reaction followed the vibrational and optical spectra of this intermediate, denoted M-OH*. However, these inherently kinetic experiments have not been connected to the relevant thermodynamic quantities. Here we discover that picosecond optical spectra of the Ti-OH* population on lightly doped SrTiO 3 are ordered by the surface hydroxylation. A Langmuir isotherm as a function of pH extracts an effective equilibrium constant relatable to the free energy difference of the first oxygen evolution reaction step. Thus, time-resolved spectroscopy of the catalytic surface reveals both kinetic and energetic information of elementary reaction steps, which provides a critical new connection between theory and experiment by which to tailor the pathway of water oxidation and other surface reactions.

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

Real-time observation of the exchange process between H 2 O and NO in the metal–organic framework Ni-MOF-74

Molecular exchange is a common step occurring in many technological processes such as competitive adsorption, chemical separation, capture, delivery, and release. However, the underlying principle is not fully understood, especially in nanoconfined environments where the energetics and kinetics of such processes can deviate from that on flat surfaces. In this study, we unravel the mechanism of a molecular exchange process by studying the displacement of NO by H 2 O in Ni-MOF-74 in real-time using in situ infrared spectroscopy combined with ab initio calculations. We show that weakly bound H 2 O gradually displaces strongly bound NO on the metal sites by first weakening the M–N bond through forming H-bond and then moving the NO away so that it eventually desorbs. Interestingly, we further find that additional water facilitates this exchange by significantly lowering the kinetic barrier associated with this process as well as the overall energy of the final state. Although our study focuses on Ni-MOF-74, we believe that our finding and explanation of unexpected exchange phenomena—where strongly adsorbed molecules are apparently easily displaced by much weaker bound H 2 O—is applicable to a much larger group of frameworks and will be helpful in designing and improving MOFs for real-world applications where humidity is often present.

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

Phenalenyl growth reactions and implications for prenucleation chemistry of aromatics in flames

The energetics and kinetics of phenalene and phenalenyl growth reactions were studied theoretically. Rate constants of phenalene and phenalenyl H-abstraction and C 2 H 2 addition to the formed radicals were evaluated through quantum-chemical and rate-theory calculations. The obtained values, assigned to all π radicals, were tested in deterministic and kinetic Monte Carlo simulations of aromatics growth under conditions of laminar premixed flames. Kekulé and non-Kekulé structures of the polycyclic aromatic hydrocarbons (PAHs) evolving in the stochastic simulations were identified by on-the-fly constrained optimization. The numerical results demonstrated an increased PAH growth and qualitatively reproduced experimental observations of Homann and co-workers of non-decaying PAH concentrations with nearly equal abundances of even and odd carbon-atom PAHs. The analysis revealed that the PAH growth proceeds via alternating and sterically diverse acetylene and methyl HACA additions. Furthermore, the rapid and diverse spreading in the PAH population supports a nucleation model as PAH dimerization, assisted by the non-equilibrium phenomena, forming planar aromatics first and then transitioning to the PAH–PAH stacking with size.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Catalytic properties of model supported nanoparticles

Nanoparticles of late transition metals are used as catalysts and electrocatalysts for industrial chemical reactions that produce fuels, convert chemical energy to electricity and clean up pollution associated with the generation and use of these fuels. For such applications, metals are usually bonded onto the surfaces of oxide or carbon support materials. To provide the energy needed for sustained economic development, we must develop new and improved solid catalysts and electrocatalysts for a variety of reactions that take better advantage of traditional and alternate energy sources (solar, wind, biomass, etc.) and avoid serious environmental problems. Additionally, since these metals are often expensive and in limited supply (e.g., Pt), we also need to develop catalysts that do not require precious metals. As a consequence, recent years have seen a dramatic increase in research aimed at providing the basic understanding needed to develop new and improved catalysts and electrocatalysts for a variety of reactions that involve nanoparticles of late transition metals supported on oxide or carbon materials. It is therefore timely to present a special issue that focusses on Catalytic Properties of Model Supported Nanoparticles. The collection highlights some of the most exciting new directions for research in this area, and provides in depth examples of some of the most cutting-edge methods, both experimental and theoretical, for studying this class of catalysts, which provide insights into structure, mechanisms, kinetics and energetics with unprecedented accuracy and detail. Finally, as Guest Editors, we present below a few of the many excellent papers published in the collection.

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

Phase-field model of freeze casting

Directional solidification of water-based solutions has emerged as a versatile technique for templating hierarchical porous materials. However, the underlying mechanisms of pattern formation remain incompletely understood. In this work, we present a detailed derivation and analysis of a quantitative phase-field model for simulating this nonequilibrium process. The phase-field model extends the thin-interface formulation of dilute binary alloy solidification with antitrapping to incorporate the highly anisotropic energetic and kinetic properties of the partially faceted ice-water interface. This interface is faceted in the basal plane normal to the ⟨0001⟩ directions and atomically rough in other directions within the basal plane. On the basal plane, the model reproduces a linear or nonlinear relationship between the interface growth rate and the kinetic undercooling that can be linked to experimental measurements. In both cases, spontaneous parity breaking of the solidification front is observed when the preferred growth direction is aligned with the temperature gradient. This phenomenon leads to the formation of partially faceted ice lamellae that drift laterally in one of the ⟨0001⟩ directions. Here, we demonstrate that the drifting velocity of the ice lamellae is controlled by the kinetics on the basal plane and converges as the thickness of the diffuse solid-liquid interface decreases. Furthermore, we examine the effect of the form of the kinetic anisotropy, which is chosen here such that the inverse of the kinetic coefficient varies linearly from a finite value in the ⟨0001⟩ directions to zero in all other directions within the basal plane, consistent with the assumption that the interface grows in local thermodynamic equilibrium in this plane. Our results indicate that the drifting velocity of ice lamellae is not affected by the slope of this linear relation, and the radius and undercooling at the tip of an ice lamella converge at relatively small slope values. Consequently, the phase-field simulations remain quantitative with computationally tractable choices of both the interface thickness and the slope assumed in the form of the kinetic anisotropy.

Materials science↗
DOE OSTI2021

Unveiling the mechanism of phase and morphology selections during the devitrification of Al-Sm amorphous ribbon

The complex interplay between energetic and kinetic factors that governs the phase and morphology selections can originate at the earliest stage of crystallization in the amorphous parent phases. Because of the extreme difficulties in capturing the microscopic nucleation process, a detailed picture of how initial disordered structures affect the transformation pathway remains unclear. Here, we report the experimental observation of widely varying phase selection and grain size evolution during the devitrification of a homogeneous melt-spun glassy ribbon. Two different crystalline phases, θ-Al 5 Sm and ε-Al 60 Sm 11 , are found to form in the different regions of the same metallic glass ribbon during the devitrification. The grain size of ε-Al 60 Sm 11 phase shows a strong spatial heterogeneity. Coarse-grained ε-Al 60 Sm 11 phase coupled with the small volume fraction of θ-Al 5 Sm phase is preferably formed close to wheel side of the melt-spun ribbon. Combining experimental characterization and computational simulations, we show that phase selection and microstructure evolution can be traced back to different types and populations of atomic clusters that serve as precursors for the nucleation of different crystalline phases. Inhomogeneous cooling rates cause different structure orders across the glass sample during the quenching process. Our findings provide direct insight into the effect of structural order on the crystallization pathways during the devitrification of metallic glass. It also opens an avenue to study the detailed nucleation process at the atomic level using the metallic glass as a platform and suggests the opportunity of microstructure and property design via controlling the cooling process.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Atomic-Scale Computational and Experimental Investigation of Twinning Mechanisms in HCP Systems

One of the major goals of the Materials Science and Engineering community is to achieve a fundamental understanding of how alloying affects the mechanical properties of structural materials. Titanium (Ti) and its alloys are particularly in demand due to their relatively lightweight, high strength and corrosion resistance. The low-temperature ductility of hexagonal close-packed (hcp) Ti known as α- Ti is linked to twinning. The addition of alloying elements can affect the deformation mechanisms leading to the change in macro-scale mechanical properties. To understand these effects, our objective is to study and quantify the energetics and kinetics of substitutional and interstitial solutes on the deformation mechanisms of hcp alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

In-situ thermodynamics measurements at metal oxides-solution interfaces using Flow Adsorption Microcalorimetry.

Mineral-fluid interfaces are the principal sites of geochemical processes near Earth’s surface, hosting chemical reactions that play a fundamental role in (bio)geochemical cycles and in the fate and transport of anthropogenic contaminants, and that effectively control the compositions of soil and water environments. These complex interfaces are critical for our energy and environmental future. The mineral-fluid interface has been studied in an unprecedented level of detail with both experimental and computational approaches, separately and in combination. However, conspicuously missing from studies of the mineral-fluid interface are direct measurements of the energies of ion sorption and exchange. The literature on energetics and enthalpies of exchange, adsorption, dissolution, precipitation, and surface protonation reactions, especially those directly supported by experimental data, remains scarce despite their fundamental nature. The overarching goal of this project is to complete a systematic study of the thermodynamics properties of interfacial reactions at four MO surfaces (Rutile (α-TiO2), Quartz (SiO2), boehmite (γ-AlOOH) and goethite (α-FeOOH)) through the application and construction of novel flow adsorption microcalorimetry techniques and instrumentations. These unique and specialized microcalorimeters will operate at various temperatures and solution chemical compositions allowing for in-situ measurements across metal oxides and ligands of various characteristics. The overall research goal will be accomplished by completing the following three specific objectives (O): O1) Determine the energetics of surface protonation and deprotonation, ion exchange and ligand sorption reactions; O2) Investigate the surface charge thermodynamic properties under a range of temperature and solution chemical compositions; and O3) Develop predictive trends of the interplay between MO structure, surface coverage and surface reactivity. In addition to key thermodynamics parameters, calorimetric measurements provide a wealth of mechanistic information about reactions energetics and kinetics, surface charge characteristics, and structure-reactivity or selectivity relationships, all obtained in-situ and in real-time. This report includes science highlights from various projects completed over the performance period of the project. Also listed are dissemination opportunities, people supported on the grant and the impact on available physical resources and the discipline as a whole.

58 GEOSCIENCES↗
NASA NTRS1983

The physics of a single-event upset in integrated circuits: A review and critique of analytical models for charge collection

When an energetic particle (kinetic energy 0.5 MeV) originating from a radioactive decay or a cosmic ray transverse the active regions of semiconductor devices used in integrated circuit (IC) chips, it leaves along its track a high density electron hole plasma. The subsequent decay of this plasma by drift and diffusion leads to charge collection at the electrodes large enough in most cases to engender a false reading, hence the name single-event upset (SEU). The problem of SEU's is particularly severe within the harsh environment of Jupiter's radiation belts and constitutes therefore a matter of concern for the Galileo mission. The physics of an SEU event is analyzed in some detail. Owing to the predominance of nonlinear space charge effects and the fact that positive (holes) and negative (electrons) charges must be treated on an equal footing, analytical models for the ionized-charge collection and their corresponding currents as a function of time prove to be inadequate even in the simplest case of uniformly doped, abrupt p-n junctions in a one-dimensional geometry. The necessity for full-fledged computer simulation of the pertinent equations governing the electron-hole plasma therefore becomes imperative.

Vonroos, O.↗
NASA NTRS2005

Water as a matrix for life

Life is based on non-covalent interactions. They might be either specific (enzyme-substrate interactions, selective ion transport) or nonspecific (lipid-lipid and lipid-protein interactions needed for membrane integrity, fusion and division). Their strength needs to be properly tuned, and this is mediated by the solvent. If interactions are too weak, there might be undesired response to natural fluctuations of physical and chemical parameters. If they are too strong it could impede kinetics and energetics of cellular processes. Thus, the solvent must allow for balancing these interactions. Physical and chemical properties of solvent provide strong constraints for life. Water exhibits a remarkable trait that it promotes both solvophobic and solvophilic interactions. Solvophobic interactions; related to high dielectric constant of the solvent) are necessary for self-organization of matter whereas solvophilic interactions are needed to ensure solubility of polar species. Water offers a large temperature domain of stable liquid and the characteristics hydrophobic effects are a consequence of the temperature in sensitivity of essential properties of its liquid state. Water, however, is not the only liquid with these favorable properties. I will compare in detail properties of water and other pure liquids or their mixtures that have a high dielectric constant and simultaneously support self-organization. I will also discuss properties of water that are unfavorable to life (e.g. its chemical activity against polymerization reactions) and close with summarizing what are alternatives to water as a matrix of life in space.

Pohorille, Andrew↗
NASA NTRS2018

Is Water Necessary for Life?

The universality of water as the solvent for life is usually justified by its role in supporting the rich organic chemistry. It has been pointed out, however, that even richer synthetic chemistry is possible in other organic solvents. Does it mean that water is not necessary for life? Here, other, essential criteria for solvent for life that have not been sufficiently considered are discussed. In biological systems, complex molecules are not only constantly synthesized but also degraded. Solvent-mediated degradation is essential for regulating cell content, preventing overcrowding and allowing for recycling organic material. Achieving a balance between synthetic and degradative processes is facile in water, but not in many other organic liquids. Thus, the so-called “water paradox” according to which water is both necessary to life and toxic to biopolymer synthesis might not be paradoxical at all. The machinery of life is based on non-covalent interactions that do not involve making or breaking chemical bonds. Their strength needs to be properly tuned. If they are too weak, there might be undesired response to natural fluctuations of physical or chemical parameters. If they are too strong, the kinetics and energetics of cellular processes could adversely influenced. The solvent must allow for balancing these interactions, which provides strong, universal constraints on the medium for life. Water influences non-covalent interactions mainly by two mechanisms. First, it reduces strong, electrostatic interactions between molecules, chemical groups or atoms carrying electric charge or dipole. Second, it induces the hydrophobic effect, the tendency to remove non-polar (hydrophobic) molecules and groups from direct contact with aqueous solution and, instead, interact with each other. In living systems, the hydrophobic effect is largely responsible for self-organization of molecules to more complex structures, such as aggregation of lipid molecules to form biological membranes and protein folding. Water exists as stable liquid in a large temperature range, and the hydrophobic effects are a consequence of the temperature insensitivity of essential properties of its liquid state. In summary, water accomplishes an amazing feat – it reduces strong interactions between dissolved species and simultaneously increases the strength of weak interactions, bringing all of them to the right range. Once we consider not only synthetic capabilities but also other required traits of the solvent for life, no viable alternative to water is currently known.

Life↗
NASA NTRS1979

A comparison of limited-area energetic processes between observations and primitive equation model predictions

Energetic analyses of the NMC initial conditions and NMC six-layer primitive equation operational prediction model 12-hr forecast for a developing cyclone are presented. Consideration is given to the total kinetic energy, the energetics of the divergent and nondivergent flows and the baroclinic (vertical shear flow) and barotropic (vertical mean flow) components of the kinetic energy. It is found that the model initial conditions lose 10-15% of the kinetic energy at various levels compared to a limited-area multivariate statistical analysis of the observational data, leading to a decrease in the horizontal kinetic energy flux, a misrepresentation of the synoptic scale wave system in the 12-hr forecast. Similar results are obtained for the nondivergent flow, while the divergent flow energetics are not reproduced accurately by the model. The horizontal flux terms of the vertical mean and vertical shear energetics are also not found to be reproduced in the upper levels, although horizontal flux contributions to the baroclinic component are improved at middle and lower levels. Finally, vertical shear kinetic energy generation is found to be well represented in the model prediction, however kinetic energy conversion between vertical shear and mean flow is not reproduced in the lower layer.

Alpert, J. C.↗
DOE OSTI2020

Toroidal modeling of anisotropic thermal transport and energetic particle effects on stability of resistive plasma resistive wall mode

Effects of anisotropic thermal transport on the linear stability of the resistive plasma resistive wall mode (RPRWM) are investigated by the magnetohydrodynamic-kinetic hybrid code MARS-K [Liu et al., Phys. Plasmas 15, 112503 (2008)], including the kinetic contribution from energetic particles (EPs). It is found that thermal transport can further stabilize the RPRWM in the presence of drift kinetic contributions from EPs. This is different from the fluid model, which always predicts destabilization of the mode by thermal transport. Furthermore, the thermal transport effect is found to amplify the role played by an adiabatic term, associated with the radial distribution of EPs’ birth energy, in modifying the mode stability as well as the mode eigenfunction. The shape of the equilibrium profiles of EPs, in particular that of the temperature, is also found to strongly affect the mode stabilization. This profile effect is more pronounced in the absence of thermal transport. MARS-K computations show that the stabilizing effect by thermal transport is more likely to occur at slower plasma rotation and lower EP energy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Hybrid simulation of energetic particles interacting with magnetohydrodynamics using a slow manifold algorithm and GPU acceleration

The hybrid method combining particle-in-cell and magnetohydrodynamics can be used to study the interaction between energetic particles and global plasma modes. In this paper we introduce the M3D-C1-K code, which is developed based on the M3D-C1 finite element code solving the magnetohydrodynamics equations, with a newly developed kinetic module simulating energetic particles. The particle pushing is done using a new algorithm by applying the Boris pusher to the classical Pauli particles to simulate the slow-manifold of particle orbits, with long-term accuracy and fidelity. The particle pushing can be accelerated using GPUs with a significant speedup. The moments of the particles are calculated using the δƒ method, and are coupled into the magnetohydrodynamics simulation through pressure or current coupling schemes. Several linear simulations of magnetohydrodynamics modes driven by energetic particles have been conducted using M3D-C1-K with the δƒ method, including fishbone, toroidal Alfvén eigenmodes and reversed shear Alfvén eigenmodes. Good agreement with previous results from other eigenvalue, kinetic and hybrid codes have been achieved.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1979

Spatial and time domain spectral energetics in the GLAS circulation model

Zonally averaged eddy kinetic energies and time domain energetics spectra were calculated for the GLAS general circulation model. The spatial results show significant improvements in the magnitude and distribution of the eddy kinetic energy. The spectral results provide a technique for tracing when and where the model predictions diverge from observations.

Tenenbaum, J.↗
NASA NTRS2003

Interfacial Reaction Studies Using ONIOM

In this report, we focus on the calculations of the energetics and chemical kinetics of heterogeneous reactions for Organometallic vapor phase epitaxy (OMVPE). The work described in this report builds upon our own previous thermochemical and chemical kinetics studies. The first of these articles refers to the prediction of thermochemical properties, and the latter one deals with the prediction of rate constants for gaseous homolytic dissociation reactions. The calculations of this investigation are at the microscopic level. The systems chosen consisted of a gallium nitride (GaN) substrate, and molecular nitrogen (N2) and ammonia (NH3) as adsorbants. The energetics for the adsorption and the adsorbant dissociation processes were estimated, and reaction rate constants for the dissociation reactions of free and adsorbed molecules were predicted. The energetics for substrate decomposition was also computed. The ONIOM method, implemented in the Gaussian98 program, was used to perform the calculations. This approach has been selected since it allows dividing the system into two layers that can be treated at different levels of accuracy. The atoms of the substrate were modeled using molecular mechanics6 with universal force fields, whereas the adsorbed molecules were approximated using quantum mechanics, based on density functional theory methods with B3LYP functionals and 6-311G(d,p) basis sets. Calculations for the substrate were performed in slabs of several unit cells in each direction. The N2 and NH3 adsorbates were attached to a central location at the Ga-lined surface.

Cardelino, Beatriz H.↗