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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Rotation in attosecond vibronic coherence spectroscopy for molecules

Abstract Excitation or ionization of a molecule by ultrafast laser pulses can create a superposition of electronic states, whose dynamics is influenced by the interplay of electronic coherence and nuclear motion, resulting in charge migration and possibly charge transfer. Probing the vibronic coherence is therefore vital to monitoring electronic dynamics and controlling chemical reactivity, as recently demonstrated in molecules via attosecond transient absorption spectroscopy (ATAS). However, theories supporting the interpretation of ATAS experiments neglect the effects of molecular rotation, often leading to inaccurate interpretation of experimental data. Here, we develop a comprehensive theory for ATAS of molecules encompassing the entire pump-probe process. Applying the theory to N 2 , we demonstrate that the emergence of coherent signals critically depends on the consideration of molecular rotation. This work contributes to close the gap between theory and ATAS experiments, paving the way for monitoring electronic motion and controlling chemical reactivity in diverse molecular systems.

Physics↗
DOE OSTI2024

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

In this article, the structural dynamics, chemical reactivity, anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO 2 ), and lithium nitrate (LiNO 3 ), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. 2D IR, NMR, and viscosity results show that LiNO 2 exhibits longer correlation times, lower diffusivity, and nearly four times greater viscosity when compared to the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water-ion interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO 2 and LiNO 3 solutions show significantly reduced chemical reactivity with respect to lithium cations coordinating with the methyl thiocyanate when compared to the lithium halide salts.

2D IR↗
DOE OSTI2023

Crystal chemistry at high pressure

The chemistry we are taught in school, and we experience in our daily existence occurs at 1 atm. However, pressure spans an astounding 62 orders of magnitude in the Universe in going from the void of interstellar space to the crushing conditions at the center of a neutron star. The way in which pressure affects chemistry is important for Earth and planetary sciences, materials science, in understanding the extreme conditions experienced in nuclear explosions, and it may be key in addressing the future energy needs of our society. In this article we outline how the often neglected pressure variable affects chemistry, beginning from the way in which atomic energy levels are altered. This lays the foundation for understanding the unique crystal and electronic structures that emerge when matter is squeezed, as well as pressure’s effect on chemical reactivity. Finally, we give an overview of the main concepts behind conventional, or phonon-mediated, superconductivity, and describe how the pressure variable may be key in discovering and designing light-element based materials whose superconducting critical temperatures approach room temperature. Here, we discuss some of the main families of superconducting hydrides that have been predicted computationally, and the experimental successes in this exciting and rapidly developing field.

Chemical bonding↗
DOE OSTI2021

Insights into Spontaneous Solid Electrolyte Interphase Formation at Magnesium Metal Anode Surface from Ab Initio Molecular Dynamics Simulations

Spontaneous chemical reactivity at multivalent (Mg, Ca, Zn, Al) electrode surfaces is critical to solid electrolyte interphase (SEI) formation, and hence, directly affects the longevity of batteries. Here, we report an investigation of the reactivity of 0.5 M Mg(TFSI)2 in 1,2-dimethoxyethane (DME) solvent at a Mg(0001) surface using ab initio molecular dynamics (AIMD) simulations and detailed Bader charge analysis. Based on the simulations, the initial degradation reactions of the electrolyte strongly depend on the structure of the Mg(TFSI)2 species near the anode surface. At the surface, the dissociation of Mg(TFSI)2 species occurs via cleavage of the N-S bond for the solvent separated ion pair (SSIP) and via cleavage of the C-S bond for the contact ion pair (CIP) configuration. In the case of the CIP, both TFSI anions undergo spontaneous bond dissociation reactions to form atomic O, C, S, F, and N species adsorbed on the surface of the Mg anode. These products indicate that the initial SEI layer formed on the surface of the pristine Mg anode consists of a complex mixture of multiple components such as oxides, carbides, sulfides, fluorides, and nitrides. We believe that the atomic level insights gained from these simulations will lay the groundwork for the rational design of tailored and functional interphases that are critical for the success of multivalent battery technology.

Agarwal, Garvit↗
NASA NTRS2005

Pd/CeO2/SiC Chemical Sensors

The incorporation of nanostructured interfacial layers of CeO2 has been proposed to enhance the performances of Pd/SiC Schottky diodes used to sense hydrogen and hydrocarbons at high temperatures. If successful, this development could prove beneficial in numerous applications in which there are requirements to sense hydrogen and hydrocarbons at high temperatures: examples include monitoring of exhaust gases from engines and detecting fires. Sensitivity and thermal stability are major considerations affecting the development of high-temperature chemical sensors. In the case of a metal/SiC Schottky diode for a number of metals, the SiC becomes more chemically active in the presence of the thin metal film on the SiC surface at high temperature. This increase in chemical reactivity causes changes in chemical composition and structure of the metal/SiC interface. The practical effect of the changes is to alter the electronic and other properties of the device in such a manner as to degrade its performance as a chemical sensor. To delay or prevent these changes, it is necessary to limit operation to a temperature <450 C for these sensor structures. The present proposal to incorporate interfacial CeO2 films is based partly on the observation that nanostructured materials in general have potentially useful electrical properties, including an ability to enhance the transfer of electrons. In particular, nanostructured CeO2, that is CeO2 with nanosized grains, has shown promise for incorporation into hightemperature electronic devices. Nanostructured CeO2 films can be formed on SiC and have been shown to exhibit high thermal stability on SiC, characterized by the ability to withstand temperatures somewhat greater than 700 C for limited times. The exchanges of oxygen between CeO2 and SiC prevent the formation of carbon and other chemical species that are unfavorable for operation of a SiC-based Schottky diode as a chemical sensor. Consequently, it is anticipated that in a Pd/CeO2/SiC Schottky diode, the nanostructured interfacial CeO2 layer would contribute to thermal stability and, by contributing to transfer of electrons, would also contribute to sensitivity.

Lu, Weijie↗
DOE OSTI2024

Cavity Controlled Upconversion in CdSe Nanoplatelet Polaritons

Exciton-polaritons provide a versatile platform for investigating quantum electrodynamics effects in chemical systems, such as polariton-altered chemical reactivity. However, using polaritons in chemical contexts will require a better understanding of their photophysical properties under ambient conditions, where chemistry is typically performed. Here, we used cavity quality factor to control strong light–matter interactions and in particular the excited state dynamics of colloidal CdSe nanoplatelets (NPLs) coupled to a Fabry– Pérot optical cavity. With increasing cavity quality factor, we observe significant population of the upper polariton (UP) state, exemplified by the rare observation of substantial UP photoluminescence (PL). Excitation of the lower polariton (LP) states results in upconverted PL emission from the UP branch due to efficient exchange of population between the LP, UP and the reservoir of dark states present in collectively coupled polaritonic systems. In addition, we measure time scales for polariton dynamics ~100 ps, implying great potential for NPL based polariton systems to affect photochemical reaction rates. State-of-the-art quantum dynamical simulations show outstanding quantitative agreement with experiments, and thus provide important insight into polariton photophysical dynamics of collectively coupled nanocrystal-based systems. These findings represent a significant step toward the development of practical polariton photochemistry platforms.

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

Exploration of Fuel Property Impacts on the Combustion of Late Post Injections Using Binary Blends and High-Reactivity Ether Bioblendstocks

In this study, the impacts of fuel volatility and reactivity on combustion stability and emissions were studied in a light-duty single-cylinder research engine for a three-injection catalyst heating operation strategy with late post-injections. Here, N-heptane and blends of farnesane/2,2,4,4,6,8,8-heptamethylnonane were used to study the impacts of volatility and reactivity. The effect of increased chemical reactivity was also analysed by comparing the baseline #2 diesel operation with a pure blend of mono-ether components (CN > 100) representative of potential high cetane oxygenated bioblendstocks and a 25 vol.% blend of the mono-ether blend and #2 diesel with a cetane number (CN) of 55. At constant reactivity, little to no variation in combustion performance was observed due to differences in volatility, whereas increased reactivity improved combustion stability and efficiency at late injection timings. Fuels with higher reactivity were found to reduce engine-out hydrocarbon and carbon monoxide emissions while also achieving stable combustion at post-injection timings later than those achievable with #2 diesel fuel. The pure ether blend had the latest achievable post-injection timing of +30.5 CAD while still maintaining stable combustion (coefficient of variation of gross-indicated mean effective pressure < 5%). With post-injection timing adjusted to achieve a matched exhaust temperature of 300 °C, the ether-diesel CN 55 blend was observed to have slightly higher thermal efficiency in comparison to the baseline #2 diesel fuel. The results also indicate that cetane number may serve as a good indicator of combustion characteristics at late injection timings used for aftertreatment thermal management operation.

09 BIOMASS FUELS↗
NASA NTRS2008

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

West, William↗
DOE OSTI2022

Femtosecond ultraviolet laser absorption spectroscopy for simultaneous measurements of temperature and OH concentration

This Letter reports a femtosecond ultraviolet laser absorption spectroscopy (fs-UV-LAS) for simultaneous in situ measurements of temperature and species. Here, this fs-UV-LAS technique was demonstrated based on X 2 Π-A 2 Σ + transitions of OH radicals near 308 nm generated in low temperature plasmas and flames. The fs-UV-LAS technique has revealed three major diagnostic benefits. First, a series of absorption features within a spectral bandwidth of ~3.2 nm near 308 nm were simultaneously measured and then enabled simultaneous multi-parameter measurements with enhanced accuracy. The results show that the temperature and OH concentration could be measured with accuracy enhanced by 29–88% and 58–91%, respectively, compared to those obtained with past two-narrow-line absorption methods. Second, an ultrafast time resolution of ~120 picoseconds was accomplished for the measurements. Third, due to the large OH X 2 Π-A 2 Σ + transitions in the UV range, a simple single-pass absorption with a 3-cm path length was allowed for measurements in plasmas with low OH number density down to ~2 × 10 13 cm –3 . Also due to the large OH UV transitions, single-shot fs absorption measurements were accomplished in flames, which was expected to offer more insights into chemically reactive flow dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Chemical factors controlling the behaviour of oxide cathodes in batteries

Oxide cathodes enable high-energy lithium-ion and sodium-ion batteries, with their performances fundamentally governed by three interrelated chemical factors: electronic configuration, chemical bonding, and chemical reactivity. Here, we illustrate how these factors dictate the redox energy, structural stability, ionic and electronic transport, and interfacial behavior in both layered oxide and polyanion oxide cathodes. We discuss how crystal-field effects and octahedral-site stabilization energies influence cation migration, and how inductive effects tune bond covalency and operating voltages. We also explain how chemical bonding governs thermal stability, gas evolution, and first-cycle capacity loss, and how alignment of transition-metal redox band with the oxygen 2p band determines electrolyte reactivity. Comparison between lithium and sodium layered oxides further reveals how differences in Li-O and Na-O bond ionicity affect chemical reactivity. Finally, we outline strategies including compositional tuning, surface doping, and electrolyte optimization, and emphasize how high-throughput, data-driven approaches in guiding the design of next-generation oxide cathodes.

25 ENERGY STORAGE↗
NASA NTRS1995

OMV/VTE variable thrust engine analysis

The objective of the present work is to develop a predictive CFD based analytical tool for the Variable Thrust Engine (VTE) in the Orbital Maneuvering Vehicle (OMV). This objective is being accomplished within the framework of the Los Alamos KIVA computer code for chemically reactive flows with sprays. For the OMV application, the main structure of KIVA is to be retained while reformulating many of the phenomenological submodels, enhancing some of the numerics, and adding more features. The analytical model consists of the general conservation equations for two-phase reactive flows and of submodels for turbulence, chemical reactions, and bipropellant sprays. Tailoring this model to the OMV engine brings about the added complexities of combustion and flow processes that occur in a liquid hypergolic propellant rocket chamber. This report exposes the foundation upon which the analytical tool is being constructed and developed. Results from a cursory computational exercise involving the simulation of the flow and combustion processes in a hypothetical N2H4/N204 rocket engine thrust chamber is presented and discussed.

Larosillere, L.↗
NASA NTRS1989

OMV/VTE variable thrust engine analysis

The objective of the present work is to develop a predictive CFD based analytical tool for the variable thrust engine (VTE) in the orbital maneuvering vehicle (OMV). This objective is being accomplished within the framework of the Los Alamos KIVA computer code for chemically reactive flows with sprays. For the OMV application, the main structure of KIVA is to be retained while reformulating many of the phenomenological submodels, enhancing some of the numerics, and adding more features. The analytical model consists of the general conservation equations for two phase reactive flows and of submodels for turbulence, chemical reactions, and bipropellant sprays. Tailoring this model to the OMV engine brings about the added complexities of combustion and flow processes that occur in a liquid hypergolic propellant rocket chamber. This report exposes the foundation upon which the analytical tool is being constructed and developed. Results from a cursory computational exercise involving the simulation of the flow and combustion processes in a hypothetical N2H4/N2O4 rocket engine thrust chamber is presented and discussed.

Larosillere, Louis↗
NASA NTRSDate not supplied

Bio-inspired Surface Structures to Mitigate Interfacial Particle Adhesion and Erosion - A Review

Lunar dust known as regolith is a huge challenge for lunar exploration missions. Formed over millennia by a complex process involving impacts of meteoroids and micrometeoroids on the lunar surface, lunar dust is porous, highly abrasive with sharp jagged edges, chemically reactive, electrostatically charged and sometimes magnetic. The chemical composition and thickness of the dust layer also varies in different regions of the lunar surface. From samples obtained by previous lunar missions, the average particle size is below 100 microns. This dust has the tendency to strongly adhere to any exposed surfaces, and often degrades the material functionality to eventually cause failure. Any material on the lunar surface is also subject to harsh temperature cycles ranging from -178 ̊C to + 123 ̊C and extreme ultraviolet radiation. While on the lunar surface, different classes of materials would be required for different applications. Advanced materials have been and will be used throughout the lunar lander, habitat, and mission equipment. Examples include: polymeric materials for astronaut protective clothing; metals and ceramics for the lunar lander legs and habitats, and excavating equipment; and semiconductors for solar panels and on-board electronics. In all these applications, the surfaces of the materials are expected or understood to be exposed to the extreme lunar environment condition that includes the regolith dust. During the Apollo missions, the dust clung to and abraded the astronaut’s suits, degraded seals, optics, clogged sensors and reduced performance of thermal radiators. The lunar dust adheres to the surface by various mechanisms, which include electrostatic and Coulombic interactions, Van-der-Waals forces, magnetic forces, mechanical interlocking, chemical bonding and donor-acceptor interactions. There are three primary strategies for developing technologies to minimize the lunar dust adhesion: active, passive and a combination of active and passive. In the active approach, an external energy is needed to prevent or remove particles from collecting on the surface. Mechanically powered brushes and electrodynamic dust screens are two examples. In the passive approach, no external power is needed, and the material surface properties are able to mitigate dust adhesion. A well-known example of this strategy is the low work function coatings for non-stick surfaces. In most cases a combination of active and passive methods might be needed to optimally manage the lunar regolith. The passive method is significantly more attractive as it does not require any external power or an additional control subsystem. These approaches optimize the mission payload and reduce risk. Surface modification to minimize the dust adhesion is thus very important to lunar missions. Here, naturally evolved surface structures might provide guidance for solutions. There are several factors that have to be considered for minimizing particle adhesion to a surface. These include the substrate material properties, surface topography, chemistry, and the characteristics of the adhering particles. When engineering a surface, the substrate material chosen would be dependent on the needs of the application. Tailoring the surface microstructure or chemistry opens up more possibilities for its optimal utilization

Lunar Dust↗
DOE OSTI2020

Prediction of organic homolytic bond dissociation enthalpies at near chemical accuracy with sub-second computational cost

Bond dissociation enthalpies (BDEs) of organic molecules play a fundamental role in determining chemical reactivity and selectivity. However, BDE computations at sufficiently high levels of quantum mechanical theory require substantial computing resources. In this paper, we develop a machine learning model capable of accurately predicting BDEs for organic molecules in a fraction of a second. We perform automated density functional theory (DFT) calculations at the M06-2X/def2-TZVP level of theory for 42,577 small organic molecules, resulting in 290,664 BDEs. A graph neural network trained on a subset of these results achieves a mean absolute error of 0.58 kcal mol-1 (vs DFT) for BDEs of unseen molecules. We further demonstrate the model on two applications: first, we rapidly and accurately predict major sites of hydrogen abstraction in the metabolism of drug-like molecules, and second, we determine the dominant molecular fragmentation pathways during soot formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2006

Thirty Years After: The Science of the Viking Program and the Discovery of a 'New Mars'

Viking discovered a Mars that was very different from the Mars found by Mariner 4, 6 and 7. The new, exciting, more Earth-like Mars was hinted at by the Mariner 9 orbiter and confirmed by Viking. Viking discovered some very fundamental things about Mars. Viking discovered the presence of nitrogen in the atmosphere. A key ingredient needed for life. Viking made the first measurements of the isotopic composition of carbon, oxygen, nitrogen and the noble gases in the atmosphere of Mars. The ratio of 15N to 14N suggested that Mars may have lost more than 99% of the total mass of its atmosphere. The denser atmosphere in the past may explain the presence of flowing water earlier in the history of Mars first discovered by Mariner 9 with additional and higher spatial resolution examples provided by the Viking Orbiters. Viking did not measure organics or life at the surface of Mars. But, Viking did discover a surface unlike any other on the Solar System--a surface exhibiting very high chemical reactivity, most probably formed by the deposition of chemically active atmospheric gases, like hydrogen peroxide (H2O2) and ozone (O3), onto the surface of Mars.

Levine, Joel S.↗
DOE OSTI2021

Importance of Engineered and Learned Molecular Representations in Predicting Organic Reactivity, Selectivity, and Chemical Properties

Machine-readable chemical structure representations are foundational in all attempts to harness machine learning for the prediction of reactivities, selectivities, and chemical properties directly from molecular structure. The featurization of discrete chemical structures into a continuous vector space is a critical phase undertaken before model selection, and the development of new ways to quantitatively encode molecules is an active area of research. Here, we highlight the application and suitability of different representations, from expert-guided “engineered” descriptors to automatically “learned” features, in different prediction tasks relevant to organic and organometallic chemistry, where differing amounts of training data are available. These tasks include statistical models of stereo- and enantioselectivity, thermochemistry, and kinetics developed using experimental and quantum chemical data. The use of expert-guided molecular descriptors provides an opportunity to incorporate chemical knowledge, domain expertise, and physical constraints into statistical modeling. In applications to stereoselective organic and organometallic catalysis, where data sets may be relatively small and 3D-geometries and conformations play an important role, mechanistically informed features can be used successfully to obtain predictive statistical models that are also chemically interpretable. We provide an overview of several recent applications of this approach to obtain quantitative models for reactivity and selectivity, where topological descriptors, quantum mechanical calculations of electronic and steric properties, along with conformational ensembles, all feature as essential ingredients of the molecular representations used. Alternatively, more flexible, general-purpose molecular representations such as attributed molecular graphs can be used with machine learning approaches to learn the complex relationship between a structure and prediction target. This approach has the potential to out-perform more traditional representation methods such as “hand-crafted” molecular descriptors, particularly as data set sizes grow. One area where this is particularly relevant is in the use of large sets of quantum mechanical data to train quantitative structure–property relationships. A general approach toward curating useful data sets and training highly accurate graph neural network models is discussed in the context of organic bond dissociation enthalpies, where this strategy outperforms regression using precomputed descriptors. Finally, we describe how graph neural network predictions can be incorporated into mechanistically informed statistical models of chemical reactivity and selectivity. Once trained, this approach avoids the expensive computational overhead associated with quantum mechanical calculations, while maintaining chemical interpretability. We illustrate examples for which fast predictions of bond dissociation enthalpy and of the identities of radicals formed through cleavage of a molecule’s weakest bond are used in simple physical models of site-selectivity and reactivity.

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

Investigation of the end-gas autoignition process in natural gas engines and evaluation of the methane number index

Engine knock and misfire are barriers to pathways leading to high-efficiency Spark-Ignited (SI) Natural Gas (NG) engines. The general tendency to knock is highly dependent on engine operating conditions and the fuel reactivity. The problem is further complicated by the wide range of chemical reactivity in pipeline quality NG, represented by the Methane Number (MN) (65< MN<95). Understanding the underlying phenomena responsible for engine knock can support the development of predictive tools capable of identifying knock onset/intensity as well as a fuel’s propensity to knock, allowing engine manufacturers to expand the knock envelope and design more efficient/robust SI NG engines. Additionally, there is an opportunity for increased efficiency by controlling levels of end-gas autoignition if this can be predicted and controlled. This work focuses on the development of a novel methodology to understand/predict a fuel’s propensity to knock. This methodology is based on the charge fraction undergoing autoignition, namely fractional end-gas autoignition (F-EGAI), and was developed based on first order laminar flame speeds and ignition delay analysis combined with a 0-D homogeneous batch reactor model. This methodology proved to be suitable to predict a fuel’s propensity to knock, even under conditions when light knock was observed. The simple modeling approach was used to explain the results from a series of MN tests with multiple NG compositions exhibiting a wide range of reactivity compositions and providing insight on why fuels of very different chemical compositions can have the same MN. Finally, a CFD model was developed was used to confirm the methodology capability and provide further insights in the physical and chemical phenomena behind end gas autoignition.

42 ENGINEERING↗