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At least 253 records · Page 14

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NASA NTRSDate not supplied

Controlling properties by chemistry in doped shape memory alloys

Shape memory alloys find increasing use in airspace applications. Using theoretical and computational methods, we investigate correlations between the selected properties and composition in doped NiTi-based shape memory alloys. Among the properties we consider relative energies, phase transition temperature, and hysteresis. We compare predictions to experimental data. Our theoretical guidance facilitates design of future alloys.

Nikolai A Zarkevich↗

NASA NTRSDate not supplied

Effects of Ambient Inert Gas Properties on Cool-Flame Combustion of Normal-Alkane Droplets in Microgravity

Cool-flame-supported quasi-steady droplet combustion was first observed during droplet combustion experiments conducted onboard the International Space Station (ISS) in the Combustion Integrated Rack (CIR) with n-alkane fuels. These cool flames, not visible to the naked eye, result from the existence of the negative-temperature-coefficient (NTC) region during the combustion n-alkane fuels when the chemical-kinetic pathways experience a transition from the low-temperature chemistry to the normal, high-temperature-controlled chemistry. In this study, we present results for the cool-flame-supported droplet burning rates and extinction diameters for n-alkane fuels (n-heptane, n-octane, n-decane, and n-dodecane) in inert-diluent-substituted ambient environments. In these ISS experiments, some of the nitrogen in the ambient gas mixture is replaced by an inert gas, namely, carbon dioxide, helium, or xenon. Different diluents were observed to exert remarkably different influences on the cool-flame combustion of fuel droplets. The results show that the cool-flame extinction diameter is drastically increased with helium dilution compared to N2, CO2 or Xe, and Xe dilution leads to longer burning with a smaller extinction diameter. Unlike hot flames, the cool-flame burning rates are controlled by the cool-flame temperature established in the NTC region by the chemical kinetics, rather than by equilibrium thermodynamics, and the thermo-physical properties of the ambient gases, which control the heat feed back to the liquid droplet. The cool-flame extinction is triggered by the instability that occurs at the low-temperature end of the NTC region, below which cool diffusion flames become statically unstable. A quasi-steady theoretical model, presented earlier, which involves a six-step reduced-chemistry mechanism, valid around the lower end of the NTC region, is shown to explain the observed experimental trends qualitatively.

microgravity↗

DOE OSTI2022

Spiers Memorial Lecture: Theory of unimolecular reactions

One hundred years ago, at an earlier Faraday Discussion meeting, Lindemann presented a mechanism that provides the foundation for contemplating the pressure dependence of unimolecular reactions. Since that time, our ability to model and predict the kinetics of such reactions has grown in leaps and bounds through the synergy of ever more sophisticated experimental studies with increasingly high level theoretical analyses. Herein, this review begins with a brief historical overview of the progress from the Lindemann mechanism to the master equation, which now provides the cornerstone for most theoretical analyses. The current status of ab initio transition state theory based implementations of the master equation is then reviewed, beginning with a discussion of the energy resolved chemical conversion rates, followed by a review of the pressure dependence of the thermal kinetics. The latter discussion focusses on the collisional energy and angular momentum transfer rates as well as the complexities of non-thermal effects and of multiple-well multiple-channel reactions. The synergy with recent state-of-the-art experiments is used to motivate these discussions. Attempts to automate the calculations are also briefly reviewed. Throughout the discussion, we provide our perspective on current understanding and continuing challenges and opportunities. One key challenge relates to the coupling of sequences of reactions, which frequently leads to deviations from the classic presumption of thermal reactants.

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 OSTI2023

Theory and Simulation of Ultrafast Multidimensional Nonlinear X-ray Spectroscopy of Molecules (Final Report)

Emerging X-ray free electron laser (XFEL) beam sources offer new types of probes of matter with unprecedented spatial and temporal resolutions. These experimental advances must be met by robust theoretical and computational tools that provide predictive modeling capacity of the underlining electronic and structural dynamics. The latter will be essential for the design of sophisticated multi-pulse experiments and for their interpretation. The proposed research effort will focus on developing cutting- edge simulation tools for nonlinear multidimensional X-ray/optical spectroscopies and aims to address key questions in Priority Research Opportunities 1 (Probing and controlling electron motion within a molecule) and 3 (Capturing rare events and intermediate states in the transformation of matter) as mentioned in the BES Roundtable Report “Opportunities for Basic Research at the Frontiers of XFEL Ultrafast Science”. XFEL multidimensional nonlinear techniques, which combine sequences of X-ray and possibly optical pulses, provide a unique experimental toolbox for probing the dynamics of core and valence electronic excitations, as well as material structure. Predictive modeling of these dynamical processes requires the combination of analytical theory for nonlinear interactions of light and matter, robust quantum-chemical methodologies for the accurate description of electronic structure of various materials, and multiscale ab initio electron and nuclear dynamics techniques operating beyond Born-Oppenheimer approximation. These challenges will be addressed with three research thrusts (i) Develop and implement theoretical apparatus for modeling a broad range of multidimensional spectroscopic techniques enabled by present and upcoming XFEL facilities. This thrust also includes the incorporation of a computational module in the DOE supported open-source NWChem computational chemistry package as well as the development of other open-source codes ready for dissemination across a broad user base; (ii) Propose and design new multi-pulse experiments that make use of the capabilities of the incoming LCLS-II facility; (iii) Perform selected applications to specific molecular systems that can be carried out at LCLS-II and demonstrate how these X-ray sources may be used to study nonadiabatic dynamics through conical interactions, electronic correlations in multi-core excitons, and charge transfer/energy transfer processes. The proposed research will be carried out by a multi-disciplinary four-institution research team which combines academia and national laboratories and spans the broad and necessary expertise in theoretical spectroscopy, nonlinear optics, quantum chemistry, molecular non-adiabatic dynamics and code development. The work will be performed in a highly interactive team environment with junior researchers shared between institutions thus cementing cross- disciplinary interactions. The developed simulation tools will be immediately deployed for XFEL facility users, both experimentalists and theorists, via freely distributed codes and databases. Altogether, this project will facilitate establishing XFEL-based multidimensional spectroscopies as a novel diagnostic tool for monitoring electronic and structural dynamics in molecular materials.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2020

Heavy quark transport: a theoretical overview

A brief overview on heavy-quark-QGP interactions is presented in this work. Theories at different momentum scales are summarized, including the flavor hierarchy of jet energy loss at high pT, hadronization and the charmed hadron chemistry at medium to low pT, and the extraction of the heavy-quark-QGP potential at low pT. Additionally, recent theoretical developments on heavy quark theories are discussed, such as multi-scale transport models of heavy quarks, probing initial state effects and cold nuclear matter effects using heavy quarks, as well as extending studies from single heavy flavor hadrons to heavy flavor jets.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS1991

UV spectroscopy of Titan's atmosphere, planetary organic chemistry and prebiological synthesis. II - Interpretation of new IUE observations in the 220-335 nm range

The theoretical model developed by McKay et al. (1989) to characterize the size distribution, thermal structure, and chemical composition of the stratospheric haze of Titan is applied to new 220-335-nm albedo measurements obtained with the long-wavelength prime camera of the IUE during August 1987. Data and model predictions are presented in extensive graphs and discussed in detail. It is shown that a simple model with particles of one size at a given altitude does not accurately reproduce the observed features in all spectral regions, but that good general agreement is obtained using a model with a uniformly mixed layer at 150-600 km and a bimodal distribution of small 'polymer' haze particles (radius less than 20 nm) and larger haze particles (radius 100-500 nm). The number densities implied by this model require, however, a mechanism such as electrostatic charging or reaction kinetics to inhibit coagulation of the smaller particles.

Courtin, Regis↗

NASA NTRS2001

Meteoric Material: An Important Component of Planetary Atmospheres

Interplanetary dust particles (IDPs) interact with all planetary atmospheres and leave their imprint as perturbations of the background atmospheric chemistry and structure. They lead to layers of metal ions that can become the dominant positively charged species in lower ionospheric regions. Theoretical models and radio occultation measurements provide compelling evidence that such layers exist in all planetary atmospheres. In addition IDP ablation products can affect neutral atmospheric chemistry, particularly at the outer planets where the IDPs supply oxygen compounds like water and carbon dioxide to the upper atmospheres. Aerosol or smoke particles from incomplete ablation or recondensation of ablated IDP vapors may also have a significant impact on atmospheric properties.

Grebowsky, Joseph M.↗

DOE OSTI2021

Bridging Aromatic/Antiaromatic Units: Recent Advances in Aromaticity and Antiaromaticity in Main-group and Transition-Metal Clusters from Bonding and Magnetic Analyses

Synthetic exploration and theoretical characterization of metal clusters are actively developing branches of modern inorganic chemistry. Advances in these areas constantly expand the rich structural diversity of viable species, allowing a detailed study of the fundamental characteristics of bench-stable compounds. In this minireview, we summarize recent achievements in synthesis and computational analyses of main-group and heterometallic clusters containing multiple aromatic/antiaromatic units. These systems range from bare clusters to ligand-decorated aggregates, providing a fundamental understanding of the aromaticity and antiaromaticity concepts in species exhibiting unprecedented shapes and composition. The review gives a comprehensive summary of bonding and magnetic response properties of such systems deciphered from the Adaptive Natural Density Partitioning (AdNDP) approach and induced magnetic field analyses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Unequal {110} Facets: The Potential Role of Intraparticle Heterogeneity and Facet Termination in Photoelectrochemical Activity of Single BiVO 4 Particles

BiVO 4 photoanodes are promising for solar water splitting, with photogenerated electrons and holes preferentially reacting at top {010} and lateral {110} facets, respectively. However, the mechanisms driving this facet-dependent reactivity remain unclear. Here, in this study, we investigate facet-dependent photocurrent and material heterogeneity using correlative scanning photoelectrochemical microscopy (SPCM), electron beam induced current (EBIC) mapping, and mid-IR scattering scanning near-field optical microscopy (s-SNOM). SPCM measurements of 62 BiVO 4 particles confirmed higher photocurrents at lateral {110} facets compared to top {010} facets, but unexpectedly revealed variations in photocurrent among lateral facets within the same particle. Variations in lateral facet surface termination could explain the intraparticle-level reactivity heterogeneity, consistent with theoretical predictions. Nano-FTIR spectroscopy and Raman microspectroscopy indicated significant materials chemistry heterogeneity within individual particles and facets that could be attributed to variations in lattice vibration distortions that enhance the overlap between Bi 6s and O 2p orbitals. The increased orbital overlap is significant as it potentially increases hole mobility in the valence band and potentially explains the lateral facet-dependent charge separation efficiency observed in photocurrent maps. Facet-dependent electrical and EBIC measurements showed no space charge regions at interfacet junctions or metal-BiVO 4 contacts under vacuum, suggesting that photogenerated holes beneath top {010} facets are unlikely to transport to lateral {110} facets to drive water/sulfite oxidation. These findings indicate the potential influence of distinct bulk properties and surface termination chemistries across different particles and facets, highlighting the importance of carefully controlling defects and surface chemistry during sample growth to optimize photocatalytic performance.

BiVO4↗

DOE OSTI2024

Improved Methods for Modeling Functional Transition Metal Compounds in Complex Environments: Ground States, Excited States, and Spectroscopies

Rapid advances in energy applications require new theory and computational models to provide guidance for interpretation of experimental results and mechanistic understanding. New theory development is necessary to treat systems of increasing complexity, size, and relevance to real applications. Functional transition metal compounds, including molecules, clusters, nanoparticles, surfaces, and solids, provide particular promise for magnetic, optical, and catalytic applications. However, such systems can be exceptionally challenging to model. To make progress in understanding and designing transition metal compounds for energy applications, theory must be able to simulate such systems in complex environments, as well as simulate the spectra of such complex systems to provide direct connections with experiment. Leveraging the independent expertise of the team’s members, this project aimed to make inroads to the theoretical and computational challenges associated with studying transition metal compounds, their reaction chemistry, photophysics and photochemistry, and response to spectroscopic interrogation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Perspective: Biochemical and Physical Constraints Associated With Preparing Thin Specimens for Single-Particle Cryo-EM

While many aspects of single-particle electron cryo-microscopy (cryo-EM) of biological macromolecules have reached a sophisticated level of development, this is not yet the case when it comes to preparing thin samples on specimen grids. As a result, there currently is considerable interest in achieving better control of both the sample thickness and the amount of area that is useful, but this is only one aspect in which improvement is needed. This Perspective addresses the further need to prevent the macromolecular particles from making contact with the air-water interface, something that can result in preferential orientation and even structural disruption of macromolecular particles. This unwanted contact can occur either as the result of free diffusion of particles during the interval between application, thinning and vitrification of the remaining buffer, or—when particles have been immobilized—by the film of buffer becoming too thin prior to vitrification. An opportunity now exists to apply theoretical and practical insights from the fields of thin-film physical chemistry and interfacial science, in an effort to bring cryo-EM sample preparation to a level of sophistication that is comparable to that of current data collection and analysis.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1985

Interstellar H3(+) - Possible detection of the 1(10)-1(11) transition of H2D

An interstellar line has been detected in emission at the expected submillimeter wavelength of the 1(10)-1(11) transition of H2D(+), the deuterated verison of the primary ion (H3/+/) in the favored ion-molecule reaction scheme for interstellar gas phase chemistry. The strength of the line is in approximate agreement with the theoretically anticipated H2D(+) abundance.

Phillips, T. G.↗

NASA NTRS1989

Infrared spectra of crystalline and glassy silicates and application to interstellar dust

The infrared spectra of crystalline minerals predicted in theoretical condensation sequences do not match the astronomical observations. Since the astronomical spectra are a closer match to glassy silicates, the authors undertook a study to measure the infrared spectra of glassy silicates that have compositions similar to silicate minerals predicted in theoretical condensation sequences. The data should support observations aimed at elucidating condensation chemistry in dust forming regions. The authors measured the mass absorption coefficients, from 2.5 to 25 microns, of ground samples of olivine, diopside, and serpentine and also smoke samples that were prepared from these minerals. The smoke samples prepared in this way are predominantly glassy with nearly the same composition as the parent minerals. The crystalline samples consisted of pure olivine ((Fe(0.1)Mg(0.9))(2)SiO(4)), serpentine, diopside. Sample purity was confirmed by x ray diffraction. Each mineral was ground for 10 hours and a measured mass of the powder was mixed with KBr powder for absorption measurements using the method of Borghesi et a. (1985). The smoke samples were prepared from the same samples used for grinding by vaporizing the minerals using pulsed laser radiation in air. The smoke samples formed by condensation of the resulting vapor. The smoke settled onto infrared transparent KRS-5 substrates and onto a quartz crystal microbalance used to obtain mass measurements. A description of the preparation method is given in Stephens (1980). The glassy diopside showed only diffuse electron diffraction peaks and hence was nearly amorphous, while the serpentine smoke showed a weak diffraction pattern corresponding to MgO. The smoke from olivine showed a weak diffraction pattern corresponding to Fe2O3 and/or Fe3O4. The mass absorption coefficients, from 2.5 to 25 microns, of crystalline diopside, olivine, and serpentine and their corresponding smoke samples are shown in figures.

Stephens, John R.↗

NASA NTRS2003

Dissociation and Recombination Effects on the Performance of Pulse Detonation Engines

This paper summarizes major theoretical results for pulse detonation engine performance taking into account real gas chemistry, as well as significant performance differences resulting from the presence of ram and compression heating. An unsteady CFD analysis, as well as a thermodynamic cycle analysis, was conducted in order to determine the actual and the ideal performance for an air-breathing pulse detonation engine (PDE) using either a hydrogen-air or ethylene-air mixture over a flight Mach number range from 0 to 4. The results clearly elucidate the competitive regime of PDE application relative to ramjets and gas turbines.

Povinelli, Louis A.↗

NASA NTRSDate not supplied

Monitoring of Ionic Silver Biocide with Capacitively-Coupled Contactless Conductivity Detection (C4D)

Monitoring of biocide dosing in spacecraft potable water systems is desirable to ensure dosing system operation and resultant microbial control. Electrolytic conductivity is linearly related to the concentration ionic silver (Ag+, the baseline biocide for future NASA missions) chemically dosed into highly purified water, and could serve as a proxy measurement. Traditional conductivity cells rely on immersed metal or graphite electrodes, which may potentially be subject to significant current-induced or auto-galvanic deposition of Ag+. Furthermore, oxide fouling may potentially induce measurement errors. Capacitively-coupled contactless conductivity detection (C4D) is a promising alternative. C4D uses electrodes placed outside an inert, non-conductive flow path, potentially mitigating such problems. We identified and purchased a commercial C4D system with claimed performance (conductivity range: 20 nS/cm to 4 µS/cm) appropriate for this application. We characterized the instrument’s performance with conductivity standards and Ag+ solutions. We began investigations considering practical and long-term detector operation, including potential current-induced deposition of conductive deposits at the tubing wall. In addition, we designed a side-stream flow system to provide liquid flow through the narrow tubing (1/16” outer diameter) required by the detector and characterized the performance of the combined C4D detector/flow system. Finally, we completed theoretical modeling of expected conductivity change with multiple dosing techniques and water chemistries.

Lance Dean Delzeit↗

DOE OSTI2025

Molecular Simulation of Functionalized Covalent Organic Framework Membranes for Inorganic Salt Separation

Covalent organic frameworks (COFs) enable molecular-level design of nanochannels for selective separation in pressure-driven membrane processes. Through variation of building blocks and, subsequently, the pore structure and chemistry, membrane performance can be tailored. This study employs nonequilibrium molecular dynamics simulations to theoretically demonstrate the tunable selectivity of COF membranes through a bottom-up functionalization approach. Water and salt transport are evaluated for six β-ketoenamine-linked COFs with varying multilayer thicknesses. For the thinnest multilayer (0.64–0.72 nm), all COFs exhibit low sodium sulfate (Na 2 SO 4 ) rejection (55–66%). However, 20 stacked sheets (6.4–7.2 nm) provide 67–98% rejection, with the sulfonated COF providing the highest Na 2 SO 4 rejection. Analysis of time-resolved ion density profiles reveals that solute rejection is primarily governed by interfacial exclusion arising from pore size and functional group chemistry. Although increasing salt rejection compromises water permeance, the permeance of all COF membranes is at least two orders of magnitude greater than that of a commercially available nanofiltration membrane. Overall, this work guides the rational design of COF membranes for aqueous salt separation.

Nanofiltration↗

DOE OSTI2026

Designing the Protocols for Programmable Ammonia Catalysis

Programmable catalysis can provide a more energy-efficient and cost-effective route to enhancing commercial ammonia production, a key process in the advancement of renewable energy technologies and the manufacture of fertilizers and basic chemicals. This work explores the computational discovery of optimal forcing protocols to drive such dynamic catalysis models. By employing matrix-free time-stepper methods, coupled with an optimization approach, that integrates Bayesian optimization with a Bayesian continuation strategy to efficiently discover the periodic steady states of such periodically forced systems, we enable the discovery of complex optimal catalyst strain waveforms, while ensuring robust solver convergence. We demonstrate the flexibility of our approach to discover optimized forcing protocols under varying physical constraints on strain modulation or other catalyst operating parameters. We show that these can have a temporal structure more complex than simple step functions. In order to detect undesirable catalytic loops that may correlate with overall reduced performance, we perform a study using graph-theoretical analysis to investigate the dynamics of catalytic kinetic networks formed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗