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The report discusses modeling gas-grain chemistry with ab initio quantum chemical cluster calculations which include heterogeneous hydrogenation of CO and H2CO on icy grain mantles, and ammonia-catalyzed, water-enhanced polymerization of formaldehyde in laboratory studies of astrophysical ices.
We have carried out extensive ab initio calculations of the electronic structure of methane, and these results are used to compute vibrational energy levels. We include basis set extrapolations, core-valence correlation, relativistic effects, and Born-Oppenheimer breakdown terms in our calculations. Our ab initio predictions of the lowest lying levels are superb.
NASA's future missions demand high energy density batteries. Current state-of-the-art lithium-ion batteries (LIBs) reach the specific energy capacity limits (<250 Wh/kg), thus new electrochemical storage technologies are needed to meet NASA's future mission requirement of >400 Wh/kg. Battery chemistries with higher theoretical energy densities in particular, Li-metal based battery chemistries such as Li-air, are being actively pursued, but there remains a number of issues to be solved. Development of advanced and optimized air cathodes will be crucial for improving capacity retention and cycle life of Li-air battery. The microstructure of carbon substrates and the catalytic oxygen reduction of the air-cathode play critical roles in the electrochemical performance in Li-air batteries. With the development and proper design of air cathodes, the energy efficiency and energy density can be enhanced significantly. In this presentation, the results of advanced permeable air cathodes design with different substrates such as 2D carbon paper or carbon cloth, vs 3D graphene or metal foam, different high surface area carbon materials and incorporation with catalysts on oxygen reduction reactions, different porosity controlling of air cathode as well the additives in electrolyte will be presented. The cycling and rate capability performance of these air-cathodes in the Li-air cells will be discussed as well.
Future space vehicles returning from distant missions or high earth orbits may enter the upper regions of the atmosphere and use aerodynamic drag to reduce their velocity before they skip out of the atmosphere and enter low earth orbit. The Aeroassist Flight Experiment (AFE) is designed to explore the special problems encountered in such entries. A computer code was developed to calculate the radiative transport along line-or-sight in the general 3-D flow field about an arbitrary entry vehicle, if the temperatures and species concentrations along the line-of-sight are known. The radiative heating calculation at the stagnation point of the AFE vehicle along the entry trajectory was performed, including a detailed line-by-line accounting of the radiative transport in the vacuum ultraviolet (below 200 nm) by the atomic N and O lines. A method was developed for making measurements of the haze particles in the Titan atmosphere above 200 km altitude. Several other tasks of a continuing nature, to improve the technical ability to calculate the nonequilibrium gas dynamic flow field and radiative heating of entry vehicles, were completed or advanced.
Over the last five years substantial progress has been made in defining the realm of new chlorine chemistry in the polar stratosphere. Application of existing experimental techniques to potentially important chlorine-containing compounds has yielded quantitative kinetic and spectroscopic data as well as qualitative mechanistic insights into the relevant reactions.
The study of the outer envelopes of cool evolved stars has become an active area of research. The physical properties of CS envelopes are presented. Observations of many wavelengths bands are relevant. A summary of observations and a discussion of theoretical considerations concerning the chemistry are summarized. Recent theoretical considerations show that the thermal equilibrium model is of limited use for understanding the chemistry of the outer CS envelopes. The theoretical modeling of the chemistry of CS envelopes provides a quantitive test of chemical concepts which have a broader interest than the envelopes themselves.
Results are presented on the following:(A) Ab initio quantum chemical studies of reactions in astrophysical ices.Theoretical electronic structure calculations were used to investigate reactions between formaldehyde (H2CO) and both hydrogen cyanide (HCN) and isocyanide (HNC) in search of other favorable reactions such as ammonia-formaldehyde addition, which was found in a recent theoretical study to be strongly enhanced when it occurs within cold ices.The present study examines further reactions between this product and H2CO in ices.(B) Heterogeneous hydrogenation of CO and H2CO on icy grain mantles.Formaldehyde (H2CO) and methanol (CH30H) are thought to be produced in the interstellar medium by the successive hydrogenation of carbon monoxide (CO) on grain surfaces. In the gas phase, the steps in which H adds to CO and H2CO possess modest barriers and are too inefficient to account for the observed abundances. Recent laboratory work has confirmed that formaldehyde and methanol are formed when H atoms are deposited on CO ice at 12 K. The present study employed ab initio quantum chemical calculations to investigate the impact of water ice on the sequential hydrogenation of CO.(C) Ice-bound condensed-phase reactions involving formic acid (HCOOH), methylenimine (CH2NH), hydrogen cyanide (HCN), hydrogen isocyanide (HNC), and ammonia ( 3) were investigated in order to characterize possible pathways to larger organic species that are efficient at the cold temperatures prevalent in cometary nuclei and the interstellar medium. (D) Pathways to glycine and other amino acids in ultraviolet-irradiated ices determined via quantum chemical modeling.(E) Photoionization in ultraviolet processing of astrophysical ice analogs at cryogenic temperatures.
Current theoretical models of solar nebula chemistry which take into account the interplay between chemistry and dynamics are presented for the abundant reactive volatile elements including hydrogen, carbon, nitrogen, oxygen, and sulfur. Results of these models indicate that, in the solar nebula, the dominant carbon and nitrogen gases were CO and NO, whereas, in giant planet subnebulae, the dominant carbon and nitrogen gases were CH4 and NH3; in the solar nebula, the Fe metal grains catalyzed the formation of organic compounds from CO and H2 via the Fischer-Tropsch-type reaction. It was also found that, in solar nebula, bulk FeS formation was kinetically favorable, while FeO incorporation into silicates and bulk Fe3O4 formation were kinetically inhibited. Furthermore, clathrate formation was kinetically inhibited in the solar nebula, while it was kinetically favorable in giant planet subnebulae.
Theoretical work on dusty plasmas was conducted in three areas: collective effects in a dusty plasma, the role of dusty plasmas in cometary atmospheres, and the role of dusty plasmas in planetary atmospheres (particularly in the ring systems of the giant planets). Laboratory investigations consisted of studies of dust/plasma interactions and stimulated molecular excitation and infrared emission by charged dust grains. Also included is a list of current publications.
Laboratory experiments and theoretical modeling show that the chemistry of chlorine is fairly simple in dense interstellar clouds, with Cl and HCl as the only species whose fractional abundances are significant. The estimated fraction of gas-phase chlorine present as HCl lies between 25-65 percent, in good agreement with the recent observations of the ground state HCl transition by Blake, Keene, and Philips (1985). These results, combined with the observational limits on HCl, indicate that chlorine is not severely depleted in dense interstellar clouds.
The results of a chemical model of SO, CS, and OCS chemistry in dense clouds are summarized. The results are obtained from a theoretical study of sulfur chemistry in dense interstellar clouds using a large-scale time-dependent model of gas-phase chemistry. Among the results are the following: (1) owing to activation energy, the reaction of CS with O atoms is efficient as a loss mechanism of CS during the early phases of cloud evolution or in hot and oxygen-rich sources such as the KL nebula; (2) if sulfur is not abnormally depleted in dense clouds, then the observed abundances of SO, SO2, H2S, CS, OCS, H2CS, and SiS indicate that sulfur is mostly atomic in dense clouds; and (3) OCS is stable against reactions with neutral atoms and radicals in dense clouds.
The recent Voyager flyby of Titan produced evidence for at least nine organic compounds in that atmosphere that are heavier than methane. Several models of Titan's atmosphere, as well as laboratory simulations, suggest the presence of organics considerably more complex that those observed. To ensure that the in situ measurements are definitive with respect to Titan's atmosphere, experiment concepts, and the related instrumentation, must be carefully developed specifically for such a mission. To this end, the possible composition of the environment to be analyzed must be bracketed and model samples must be provided for instrumentation development studies. Laboratory studies to define the optimum flight experiment and sampling strategy for a Titan entry probe are currently being conducted. Titan mixtures are being subjected to a variety of energy sources including high voltage electron from a DC discharge, high current electric shock, and laser detonation. Gaseous and solid products are produced which are then analyzed. Samples from these experiements are also provided to candidate flight experiments as models for instrument development studies. Preliminary results show that existing theoretical models for chemistry in Titan's atmosphere cannot adequetely explain the presence and abundance of all trace gases observed in these experiments.
Variational methods have proven invaluable in theoretical physics and chemistry, both for bound state problems and for the study of collision phenomena. The application of the Schwinger variational (SV) method to e-molecule collisions and molecular photoionization has been reviewed previously. The present chapter discusses the implementation of the SV method as applied to e-molecule collisions. Since this is not a review of cross section data, cross sections are presented only to server as illustrative examples. In the SV method, the correct boundary condition is automatically incorporated through the use of Green's function. Thus SV calculations can employ basis functions with arbitrary boundary conditions. The iterative Schwinger method has been used extensively to study molecular photoionization. For e-molecule collisions, it is used at the static exchange level to study elastic scattering and coupled with the distorted wave approximation to study electronically inelastic scattering.
Variational methods have proven invaluable in theoretical physics and chemistry, both for bound state problems and for the study of collision phenomena. For collisional problems they can be grouped into two types: those based on the Schroedinger equation and those based on the Lippmann-Schwinger equation. The application of the Schwinger variational (SV) method to e-molecule collisions and photoionization has been reviewed previously. The present chapter discusses the implementation of the SV method as applied to e-molecule collisions.
Astronomical observations, theoretical modeling, laboratory simulation and analysis of extraterrestrial material have enhanced our knowledge of the inventory of organic matter in the interstellar medium (ISM) and on small bodies such as comets and asteroids (Ehrenfreund & Charnley 2000). Comets, asteroids and their fragments, meteorites and interplanetary dust particles (IDPs), contributed significant amounts of extraterrestrial organic matter to the young Earth. This material degraded and reacted in a terrestrial prebiotic chemistry to form organic structures that may have served as building blocks for life on the early Earth. In this talk I will summarize our current understanding of the organic composition and chemistry of interstellar clouds. Molecules of astrobiological relevance include the building blocks of our genetic material: nucleic acids, composed of subunits such as N-heterocycles (purines and pyrimidines), sugars and amino acids. Signatures indicative of inheritance of pristine and modified interstellar material in comets and meteorites will also be discussed.
An event in which electronic insulation consisting of polytetrafluoroethylene undergoes thermodegradation on the Space Station Freedom is considered experimentally and theoretically from the initial chemistry and convective transport through pulmonary deposition in humans. The low-gravity enviroment impacts various stages of event simulation. Vapor-phase and particulate thermodegradation products were considered as potential spacecraft contaminants. A potential pathway for the production of ultrafine particles was identified. Different approaches to the simulation and prediction of contaminant transport were studied and used to predict the distribution of generic vapor-phase products in a Space Station model. A lung transport model was used to assess the pulmonary distribution of inhaled particles, and, finally, the impact of adaptation to low gravity on the human response to this inhalation risk was explored on the basis of known physiological modifications of the immune, endocrine, musculoskeletal and pulmonary systems that accompany space flight.
Interstellar chemistry provides a natural laboratory for studying exotic species and processes at densities, temperatures, and reaction rates. that are difficult or impractical to address in the laboratory. Thus, many chemical reactions considered too sloe by the standards of terrestrial chemistry, can be 'observed and modeled. Curious proposals concerning the nature and chemistry of complex interstellar organic molecules will be described. Catalytic reactions on "rain surfaces can, in principle, lead to a lame variety of species and this has motivated many laboratory and theoretical studies. Gas phase processes may also build lame species in molecular clouds. Future laboratory data and computational tools needed to construct accurate chemical models of various astronomical sources to be observed by Herschel and ALMA will be outlined.
Interstellar chemistry provides a natural laboratory for studying exotic species and processes at densities, temperatures, and reaction rates, that are difficult or impractical to address in the laboratory. Thus, many chemical reactions considered too slow by the standards of terrestrial chemistry, can be 'observed' and modeled. Various proposals concerning the nature and chemistry of complex interstellar organic molecules will be described. Catalytic reactions on grain surfaces can, in principle, lead to a large variety of species and this has motivated many laboratory and theoretical studies. Gas phase processes may also build large species in molecular clouds. Future laboratory data and computational tools needed to construct accurate chemical models of various astronomical sources to be observed by Herschel and ALMA will be outlined