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At least 73 records · Page 4

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NASA NTRS1979

Minor constituents in the stratosphere and mesosphere

A review of the research in minor constituents in the stratosphere and mesosphere, carried out between 1975 and 1978, is presented. Much of the theoretical research was done with the aid of one-dimensional models. Different aspects of these models are discussed. Measurements of the chlorofluoromethanes, hydrochloric acid, nitric oxide, nitrous oxide, and hydrogen oxide were conducted. It is noted that the hydrogen oxides are now assuming a larger role in stratospheric photochemistry than have been postulated before. The effect of water vapor and the hydrogen oxides on the overall chemistry of the stratosphere was investigated theoretically, along with the possible relationship between solar activity and atmospheric ozone. The mesosphere study included ozone, water vapor, nitric oxide, and odd nitrogen investigations.

Hudson, R. D.↗

NASA NTRS1978

Organic chemistry on Titan

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

Chang, S.↗

NASA NTRSDate not supplied

Dry Pressed, High Areal Loading Electrode Architectures Enabled by Holey Graphene

For future electric aviation, advanced battery cell chemistry beyond lithium ion batteries are required to meet mission requirements. High energy density battery concepts such as lithium-sulfur (Li-S) and lithiumoxygen (Li-O2) chemistries are being intensively investigated to realize their extraordinary theoretical promise in terms of energy density. Most fabrication methods of cathodes for these novel battery chemistries followed a conventional approach. In this approach, the active material is mixed with a polymer binder and a conductive carbon in a high-boiling organic solvent to form a slurry, followed by casting onto a current collector and solvent evaporation. The process is usually lengthy and poses environmental hazards due to the use of organic solvents.

Lin Yi↗

NASA NTRS1977

The effects of thermospheric winds and chemistry in the diurnal variations of thermospheric species

The reported investigation considers on the basis of a theoretical model, the diurnal variations of the thermospheric composition (H, He, O, O2, and Ar) in terms of thermal expansion with diffusive equilibrium and transport effects associated with thermospheric winds, chemistry, and exospheric flow. The theoretical results are compared with satellite composition data which indicate that the fundamental diurnal tide can be reasonably well understood. It is found that winds are only important for molecular oxygen below 180 km, while thermal expansion due to the larger mass is relatively more important for O2 than for O. Distinct from O, photodissociation and in particular photoionization of O2 are very significant for molecular oxygen.

Mayr, H. G.↗

NASA NTRS1972

'Thunder' - Shock waves in pre-biological organic synthesis.

Theoretical study of the gasdynamics and chemistry of lightning-produced shock waves in a postulated primordial reducing atmosphere. It is shown that the conditions are similar to those encountered in a previously performed shock-tube experiment which resulted in 36% of the ammonia in the original mixture being converted into amino acids. The calculations give the (very large) energy rate of about 0.4 cal/sq cm/yr available for amino acid production, supporting previous hypotheses that 'thunder' could have been responsible for efficient large-scale production of organic molecules serving as precursors of life.

Bar-Nun, A.↗

NASA NTRS1982

Rate constant for the reaction NH2 + NO from 216 to 480 K

The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

Stief, L. J.↗

NASA NTRS1984

Theoretical research program to predict the properties of molecules and clusters containing transition metal atoms

The primary focus of this research has been the theoretical study of transition metal (TM) chemistry. A major goal of this work is to provide reliable information about the interaction of H atoms with iron metal. This information is needed to understand the effect of H atoms on the processes of embrittlement and crack propagation in iron. The method in the iron hydrogen studies is the cluster method in which the bulk metal is modelled by a finite number of iron atoms. There are several difficulties in the application of this approach to the hydrogen iron system. First the nature of TM-TM and TM-H bonding for even diatomic molecules was not well understood when these studies were started. Secondly relatively large iron clusters are needed to provide reasonable results.

Walch, S.↗

NASA NTRS1984

Review of solar fuel-producing quantum conversion processes

The status and potential of fuel-producing solar photochemical processes are discussed. Research focused on splitting water to produce dihydrogen and is at a relatively early stage of development. Current emphasis is primarily directed toward understanding the basic chemistry underlying such quantum conversion processes. Theoretical analyses by various investigators predict a limiting thermodynamic efficiency of 31% for devices with a single photosystem operating with unfocused sunlight at 300 K. When non-idealities are included, it appears unlikely that actual devices will have efficiencies greater than 12 to 15%. Observed efficiencies are well below theoretical limits. Cyclic homogeneous photochemical processes for splitting water have efficiencies considerably less than 1%. Efficiency can be significantly increased by addition of a sacrificial reagent; however, such systems are no longer cyclic and it is doubtful that they would be economical on a commercial scale. The observed efficiencies for photoelectrochemical processes are also low but such systems appear more promising than homogeneous photochemical systems. Operating and systems options, including operation at elevated temperature and hybrid and coupled quantum-thermal conversion processes, are also considered.

Peterson, D. B.↗

NASA NTRS1997

Model For Dense Molecular Cloud Cores

We present a detailed theoretical model for the thermal balance, chemistry, and radiative transfer within quiescent dense molecular cloud cores that contain a central protostar. In the interior of such cores, we expect the dust and gas temperatures to be well coupled, while in the outer regions CO rotational emissions dominate the gas cooling and the predicted gas temperature lies significantly below the dust temperature. Large spatial variations in the gas temperature are expected to affect the gas phase chemistry dramatically; in particular, the predicted water abundance varies by more than a factor of 1000 within cloud cores that contain luminous protostars. Based upon our predictions for the thermal and chemical structure of cloud cores, we have constructed self-consistent radiative transfer models to compute the line strengths and line profiles for transitions of (12)CO, (13)CO, C(18)O, ortho- and para-H2(16)O, ortho- and para-H2(18)O, and O I. We carried out a general parameter study to determine the dependence of the model predictions upon the parameters assumed for the source. We expect many of the far-infrared and submillimeter rotational transitions of water to be detectable either in emission or absorption with the use of the Infrared Space Observatory (ISO) and the Submillimeter Wave Astronomy Satellite. Quiescent, radiatively heated hot cores are expected to show low-gain maser emission in the 183 GHz 3(sub 13)-2(sub 20) water line, such as has been observed toward several hot core regions using ground-based telescopes. We predict the (3)P(sub l) - (3)P(sub 2) fine-structure transition of atomic oxygen near 63 micron to be in strong absorption against the continuum for many sources. Our model can also account successfully for recent ISO observations of absorption in rovibrational transitions of water toward the source AFGL 2591.

Doty, Steven D.↗

NASA NTRS2002

Ab initio calculations of anharmonic vibrational spectroscopy for hydrogen fluoride (HF)n (n = 3, 4) and mixed hydrogen fluoride/water (HF)n(H2O)n (n = 1, 2, 4) clusters

Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n, with n = 3, 4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n = 1, 2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the Moller-Plesset (MP2) potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.

Water/chemistry↗

NASA NTRS1994

Global Ozone and Reactive Nitrogen : Composition, Chemistry and Sources

Ozone plays a central role in the chemistry of the atmosphere both as an ultraviolet shield and as a source of hydroxyl radicals (OH), a potent initiator of atmospheric chemistry. There is evidence to suggest that the ozone abundance in the troposphere (0-10 km) has doubled since the industrial revolution and continues to increase to date. The principle reason for this increase is thought to be the increasing emissions of nitrogen oxides (NO(x)) from anthropogenic activities. Although NO(x) is highly reactive and its products such as HN03 are easily removed by deposition, it now appears that its chemistry is quite complex and it can be transported over long distances via its conversion to a variety of nitrates and penetrates. The sources of atmospheric NO(x) include free tropospheric sources such as lightning and subsonic aircraft, as well as surface emissions which are transported to the free troposphere via convective processes. Recent experimental and theoretical studies have tried to unravel the chemistry of reactive nitrogen species, its sources, and their role in ozone formation. In this presentation we shall describe the results from these studies.

Sing, Hanwant B.↗

NASA NTRSDate not supplied

Open Science at the Onset of JWST

The characterization of a diverse set of atmospheres, ranging from brown dwarfs to hot gas giants to small temperate rocky worlds will be part of the legacy of JWST and future NASA missions. These technological innovations will enable a plethora of discoveries, unveiling a variety of new chemical and physical regimes that could even point to the first detection of life beyond Earth. However, our ability to fully interpret these results will hinge on how well we can link observations to numerous complex theoretical models that describe, for example, the chemistry and climate. An immediate demonstration of this was executed in the analysis of JWST’s very first exoplanet spectrum. An open collaboration of more than 300 students, postdocs, faculty, and researchers worldwide worked together to analyze the exquisite dataset. The result was the first identification of carbon dioxide in a planet beyond our own Solar System. I will discuss how NASA’s open science guiding principles are centered in our Early Release Science team, supporting an inclusive, transparent, and collaborative scientific process. And ultimately, I will showcase the science that was born from this open process.

Natasha Batalha↗

NASA NTRS2013

Design Issues for Using Magnetic Materials in Radiation Environments at Elevated Temperature

One of the challenges of designing motors and alternators for use in nuclear powered space missions is accounting for the effects of radiation. Terrestrial reactor power plants use distance and shielding to minimize radiation damage but space missions must economize volume and mass. Past studies have shown that sufficiently high radiation levels can affect the magnetic response of hard and soft magnetic materials. Theoretical models explaining the radiation-induced degradation have been proposed but not verified. This paper reviews the literature and explains the cumulative effects of temperature, magnetic-load, and radiation-level on the magnetic properties of component materials. Magnetic property degradation is very specific to alloy choice and processing history, since magnetic properties are very much entwined with specific chemistry and microstructural features. However, there is basic theoretical as well as supportive experimental evidence that the negative impact to magnetic properties will be minimal if the bulk temperature of the material is less than fifty percent of the Curie temperature, the radiation flux is low, and the demagnetization field is small. Keywords: Magnets, Permanent Magnets, Power Converters, Nuclear Electric Power Generation, Radiation Tolerance.

Bowman, Cheryl L.↗

NASA NTRS1997

Heterogeneous Combustion of Porous Graphite Particles in Microgravity

Recent theoretical investigations on graphite particle combustion have employed several levels of heterogeneous reaction models, ranging from global to elementary models, to describe the oxidation of carbon to gaseous products. Unlike the counterpart homogeneous reaction models, these heterogeneous reaction models are not well developed because of the difficulties associated with decoupling the physical characteristics of the solid (e.g. surface area taking part in combustion) from the chemical kinetic data. This is certainly true for porous graphite particle combustion, where heterogeneous and homogeneous reactions occur within the pores and play an important role in the overall oxidation process. As a result, there are considerable uncertainties of physical phenomena predicted using different heterogeneous kinetic models available in the literature. A good example, discussed later in this paper, is the predicted critical particle size below which the mass burning rate becomes exponentially small. The main goal of this study is to understand the basic mechanism controlling such rapid changes in burning rates, by developing a model where physical contributions are decoupled from chemical rate constants in a consistent manner. Another important goal of the proposed study is to develop a truly intrinsic, detailed heterogeneous reaction model for porous graphite combustion at high-temperatures, and to derive a systematically reduced heterogeneous reaction model in terms of the elementary reaction rate constants of the detailed model. The validation of chemical kinetic models describing the heterogeneous and homogeneous combustion in and around a spherically symmetric porous graphite particle can be considerably simplified by experimental measurements obtained under microgravity conditions. A vital component of this study is to conduct such supporting experiments on particle burning rate and surface temperature using NASA microgravity facilities, in close coordination with the theoretical effort. The basic understanding obtained and models developed as part of this project will be useful for optimal design of coal combustion devices. These models can also be extended to investigate the role of heterogeneous chemistry on pollutant formation pathways in combustion devices. The theoretical approach developed here, with pore diffusion effects decoupled from the chemical effects, can also be extended to understand the heterogeneous combustion of other porous fuels, for example, combustion of magnesium in a CO2 environment for propulsion in the Martian atmosphere.

Chelliah, Harsha K.↗

NASA NTRSDate not supplied

Solid-state battery designed for electric aviation

The demand for higher energy density batteries increases as the demand for portable electronic devices and electric automotive increases, as well as a variety of other applications requiring substantially higher power and energy than attainable with current lithium-ion capabilities which includes the areas of high performance vehicles, military applications, and electric aviation. However, the improvement of energy density is insufficient alone for enabling electric aviation when considering the high flammability and risk of thermal runaway inherent in current state-of-the-art liquid electrolytes. The development of high energy, high power, and safe batteries are required to enable hybrid and fully electric aircraft. Next generation chemistries such as lithium-sulfur provide high theoretical specific energy density suitable for electric aviation without as strict of volumetric requirements observed in the automotive industry. However, due to the phase transition during discharge where sulfur generates a series of soluble intermediate polysulfides, which are lost to the liquid electrolyte, cause detrimental side effects, and severely limit cycle life battery performance is severely reduced. Additionally, the low electrical conductivity of sulfur requires a large amount of inactive carbon dramatically increasing parasitic mass. The dissolution issue make sulfur a desirable candidate to pair with a solid-state electrolyte in order to avoid polysulfide dissolution and shuttling. In addition, inorganic solid-electrolytes have low flammability providing the improved safety required. Combining this chemistry with a solid-state electrolyte provides a path for achieving the energy and safety required for electric aviation. The development of scalable thin solid-state electrolytes paired with lithium-sulfur chemistry will be discussed and how their development will aid in enabling a unique application.

Donald A. Dornbusch↗

NASA NTRSDate not supplied

Experimental and Theoretical Needs for the JWST Early Release Science Program on Radiative Feedback from Massive Stars (PDRs4ALL): III. A Quantum Chemistry Perspective

Massive stars disrupt their natal molecular cloud material by dissociating molecules, ionizing atoms and molecules, and heating the gas and dust. These processes drive the evolution of interstellar matter in our Galaxy and throughout the Universe from the era of vigorous star formation at z=1-3 to the present day. Much of this interaction occurs in Photo- Dissociation Regions (PDRs) where far-ultraviolet photons of these stars create a largely neutral, but warm region of gas and dust. PDR emission dominates the IR spectra of starforming galaxies and provides a unique tool to study the physical and chemical processes that are relevant for inter- and circumstellar media including diffuse clouds, molecular cloud and protoplanetary disk surfaces, and starburst galaxies. The ERS program ID1288 is dedicated to provide template data as well as data processing and analysis tools for PDRs. To this end, it will observe the Orion Bar, the proto-typical PDR situated in the nearby Orion Nebula, using NIRSpec IFU, MIRI IFU, and NIRCAM and MIRI imaging. These observations will, for the first time, spatially resolve and perform a tomography of the PDR, revealing the individual IR spectral signatures from the key zones and sub-regions within the ionized gas, the PDR, and the molecular cloud. Quantum chemistry can be used to determine molecular data such as ionization potentials, chemical reaction rates, electronic spectra, dissociation energies, channels, and branching ratios, etc. These are often used in synergy with experiment to take advantage of the strengths of each approach. An area of active research is modeling the infrared (IR) emission spectra produced by PAH molecules, including the effects of anharmonicity. This will be important in the interpretation of JWST data which will yield higher-resolution spectral data compared to Spitzer or ISO. Quantum chemistry methods can compute accurate anharmonic IR absorption spectra of PAH molecules up to about 25 C atoms, and the results have been benchmarked against high-resolution experimental spectra. These feed into a quantum Monte Carlo (QMC) approach to generate temperature-dependent anharmonic IR emission spectra and then used to generate fully anharmonic cascade emission IR spectra of PAH molecules -- the very type of spectra that JWST will observe. Work continues to extend these methods to larger PAH molecules. We will discuss the current state of this work, as well as

Timothy Lee↗

NASA NTRS1995

The effects of detailed chemistry and transport on microgravity droplet combustion

A brief overview of recent advances in the theoretical study of microgravity droplet combustion is presented. Much of this work has centered on the development and utilization of sphero-symmetric transient numerical models which consider detailed gas phase chemistry and transport as well as energy and/or species transport within a regressing condensed phase. Numerical results for microgravity combustion and vaporization of methanol, methanol/water, heptane, and heptane/hexadecane droplets are summarized along with refinements in chemical kinetics and the development of a new two-dimensional axi-symmetric model.

Marchese, A. J.↗

NASA NTRS1985

Theoretical Thermodynamics of Mixtures at High Pressures

The development of an understanding of the chemistry of mixtures of metallic hydrogen and abundant, higher-z material such as oxygen, carbon, etc., is important for understanding of fundamental processes of energy release, differentiation, and development of atmospheric abundances in the Jovian planets. It provides a significant theoretical base for the interpretation of atmospheric elemental abundances to be provided by atmospheric entry probes in coming years. Significant differences are found when non-perturbative approaches such as Thomas-Fermi-Dirac (TFD) theory are used. Mapping of the phase diagrams of such binary mixtures in the pressure range from approx. 10 Mbar to approx. 1000 Mbar, using results from three-dimensional TFD calculations is undertaken. Derivation of a general and flexible thermodynamic model for such binary mixtures in the relevant pressure range was facilitated by the following breakthrough: there exists an accurate nd fairly simple thermodynamic representation of a liquid two-component plasma (TCP) in which the Helmholtz free energy is represented as a suitable linear combination of terms dependent only on density and terms which depend only on the ion coupling parameter. It is found that the crystal energies of mixtures of H-He, H-C, and H-O can be satisfactorily reproduced by the same type of model, except that an effective, density-dependent ionic charge must be used in place of the actual total ionic charge.

Hubbard, W. B.↗