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NASA NTRS1985

ac susceptibility of thermally annealed and neutron irradiated Cu-Ni alloys

Thermal annealing and high-flux neutron irradiation are used to vary the degree of short-range atomic order in Cu-Ni alloys of composition 40, 50, and 60 at. pct Ni. The magnetic state is measured by ac magnetic susceptibility measurements. It is shown that annealing at 350 C causes significant changes in the susceptibility of all the samples. In the 50 and 60 at. pct Ni samples, the transition is broadened and extended to higher temperatures, while the 40 at. pct Ni sample changes from a paramagnetic system to a weakly ferromagnetic system. The neutron irradiation, in contrast to the thermal treatment, causes the development of smaller size cluster formations. The irradiated 60 at. pct Ni sample exhibits no change in the shape of its susceptibility curve from that of the quenched sample, whereas, the 40 pct alloy is changed, by irradiation, from a paramagnetic system to a spin-glass system.

Catchings, R. M., III↗

NASA NTRSDate not supplied

Effect of Aromaticity on Soot Formation: A Reactive Molecular Dynamics Study

This study investigates the formation of soot from n-dodecane and its blend with m-xylene under pyrolytic and low-oxygen conditions with reactive molecular dynamics (MD) simulations. ReaxFF force field is used to simulate the interactions of fuel and oxygen molecules at engine-relevant conditions (2500-3500 K and 70-75 bar). Fuel molecules with carbon atom density of 0.03 g/cm 3 are dispersed into a cube and constant temperature simulations are carried out with a Nosé-Hoover thermostat. Pyrolysis of n-dodecane and the chemical pathway towards the formation of aromatic hydrocarbons are investigated. The initial pyrolysis rate of n-dodecane is observed to be slightly higher with the addition of aromatic compounds and oxygen. While the first aromatics formed from the decomposed n-dodecane are phenyl radicals at 2500 K, decomposition of the aliphatic fuel compound is observed to be necessary to build a carbon cluster, and eventually soot. Morphological properties of the created soot particles are also analyzed. The maturity, size and aromatics content of the soot particle are slightly affected with the addition of m-xylene and oxygen at 3500 K within the 3 ns simulation time possibly due the formation of larger and more condensed aromatic rings, resulting in larger soot molecules. The outcomes of this study provide important insights into the formation mechanism of soot and its morphological characteristics depending on varying fuel concentrations at pyrolysis and low oxygen engine conditions. Results of this analysis will further contribute to the understanding of contrail formation on generated soot particles originated from the combustion of different chemical components with particle chemistry matching companion experiments.

soot formation↗

NASA NTRS2001

CFD Simulation of Liquid Rocket Engine Injectors

Detailed design issues associated with liquid rocket engine injectors and combustion chamber operation require CFD methodology which simulates highly three-dimensional, turbulent, vaporizing, and combusting flows. The primary utility of such simulations involves predicting multi-dimensional effects caused by specific injector configurations. SECA, Inc. and Engineering Sciences, Inc. have been developing appropriate computational methodology for NASA/MSFC for the past decade. CFD tools and computers have improved dramatically during this time period; however, the physical submodels used in these analyses must still remain relatively simple in order to produce useful results. Simulations of clustered coaxial and impinger injector elements for hydrogen and hydrocarbon fuels, which account for real fluid properties, is the immediate goal of this research. The spray combustion codes are based on the FDNS CFD code' and are structured to represent homogeneous and heterogeneous spray combustion. The homogeneous spray model treats the flow as a continuum of multi-phase, multicomponent fluids which move without thermal or velocity lags between the phases. Two heterogeneous models were developed: (1) a volume-of-fluid (VOF) model which represents the liquid core of coaxial or impinger jets and their atomization and vaporization, and (2) a Blob model which represents the injected streams as a cloud of droplets the size of the injector orifice which subsequently exhibit particle interaction, vaporization, and combustion. All of these spray models are computationally intensive, but this is unavoidable to accurately account for the complex physics and combustion which is to be predicted, Work is currently in progress to parallelize these codes to improve their computational efficiency. These spray combustion codes were used to simulate the three test cases which are the subject of the 2nd International Workshop on-Rocket Combustion Modeling. Such test cases are considered by these investigators to be very valuable for code validation because combustion kinetics, turbulence models and atomization models based on low pressure experiments of hydrogen air combustion do not adequately verify analytical or CFD submodels which are necessary to simulate rocket engine combustion. We wish to emphasize that the simulations which we prepared for this meeting are meant to test the accuracy of the approximations used in our general purpose spray combustion models, rather than represent a definitive analysis of each of the experiments which were conducted. Our goal is to accurately predict local temperatures and mixture ratios in rocket engines; hence predicting individual experiments is used only for code validation. To replace the conventional JANNAF standard axisymmetric finite-rate (TDK) computer code 2 for performance prediction with CFD cases, such codes must posses two features. Firstly, they must be as easy to use and of comparable run times for conventional performance predictions. Secondly, they must provide more detailed predictions of the flowfields near the injector face. Specifically, they must accurately predict the convective mixing of injected liquid propellants in terms of the injector element configurations.

Farmer, Richard↗

NASA NTRS2011

The Cosmic-Ray and Gas Content of the Cygnus Region as Measured in Gamma Rays by the Fermi Large Area Telescope

Context. The Cygnus region hosts a giant molecular-cloud complex which actively forms massive stars. Interactions of cosmic rays with interstellar gas and radiation fields make it shine at y-ray energies. Several gamma-ray pulsars and other energetic sources are seen in this direction. Aims. In this paper we analyse the gamma-ray emission measured by the Fermi Large Area Telescope in the energy range from 100 Me V to 100 Ge V in order to probe the gas and cosmic-ray content over the scale of the whole Cygnus complex. The gamma-ray emission on the scale of the central massive stellar clusters and from individual sources is addressed elsewhere. Methods. The signal from bright pulsars is largely reduced by selecting photons in their off-pulse phase intervals. We compare the diffuse gamma-ray emission with interstellar gas maps derived from radio/mm-wave lines and visual extinction data. and a global model of the region, including other pulsars and gamma-ray sources, is sought. Results. The integral H I emissivity above 100 MeV averaged over the whole Cygnus complex amounts to 12.06 +/- 0.11 (stat.) (+0.15 -0.84) (syst.J] x 10(exp -26) photons /s / sr / H-atom, where the systematic error is dominated by the uncertainty on the H I opacity to calculate its column densities. The integral emissivity and its spectral energy distribution are both consistent within the systematics with LAT measurements in the interstellar space near the solar system. The average X(sub co) N(H2)/W(sub co) ratio is found to be [1.68 +/- 0.05 (stat.) (H I opacity)] x 1020 molecules cm-2 (K km/s /r, consistent with other LAT measurements in the Local Arm. We detect significant gamma-ray emission from dark neutral gas for a mass corresponding to approx 40% of that traced by CO. The total interstellar mass in the Cygnus complex inferred from its gamma-ray emission amounts to 8(+5 -1) x 10(exp 6) Solar M at a distance of 1.4 kpc. Conclusions. Despite the conspicuous star formation activity and large masses of the interstellar clouds, the cosmic-ray population in the Cygnus complex averaged over a few hundred parsecs is similar to that of the local interstellar space.

Ackermann, M.↗

NASA NTRSDate not supplied

Optical Time Transfer for Bistatic SAR Spacecraft

A spacecraft-to-spacecraft optical time-transfer simulation has been developed as a tool for informing NASA’s Surface Deformation and Change (SDC) mission architecture. The SDC mission will combine radar images from multiple spacecraft to improve understanding of the Earth’s sea-level and landscape changes. Spacecraft must be precisely synchronized in order to create sharp radar images. Simulation of multiple spacecraft time-synchronizing via laser communication can inform technology choices of a mission by providing a picosecond-precision level estimate of clock error. This timing and ranging simulation has been combined with a radar system performance analysis pipeline. The simulated timing errors are used to predict performance of bistatic SAR systems in the presence of oscillator noise and time synchronization in accuracy. This analysis includes both analytic approximation equations from existing literature, and a numerical radar simulation to extract key system performance parameters like phase error and signal-to-noise ratio (SNR)degradation. Precision time-transfer techniques facilitate the accurate synchronization of clocks between any combination of terminals. Most time-transfer technology for comparing two clocks at different terminals use radio frequencies (RF) to measure the time delay between the sending and receiving of signals. Laser technology offers the capability to transmit high data rates with systems that are of smaller size and lower power than comparable RF systems. The clocks on independent spacecraft will have some phase and frequency errors between them that result in clock drift. The two clock models that are included in this bi-directional MATLAB simulation are a cesium-based Chip-Scale Atomic Clock (CSAC) and a rubidium-based Miniature Atomic Clock (MAC). The CSAC has flown as hardware for small satellite missions such as the University of Florida’s CHOMPTT mission. A study of example orbits, including that of NASA NASA-ISRO Synthetic Aperture Radar Mission (NISAR) mission, and lasing rates demonstrate the impact of flight configuration parameters on the synchronization error between two spacecraft. The MATLAB timing simulation uses a Runge-Kutta 4th-order method to propagate spacecraft orbits and computes the light-travel time estimate between them. The simulation outputs the estimated range and estimated clock error based on a user-defined spacecraft cluster configuration. The radar simulation and analytic approximations are applied to evaluate a potential future NASA bistatic SAR constellation architecture. In the proposed architecture, satellites follow each other in the same orbit at 800 km altitude, with a 210 km baseline. We also baseline the CSAC as an ultra stable oscillator, and use NASA’s NISAR for baseline radar system parameters to compute a clock-system introduced phase error of 5.6 degrees without synchronization by frequent time transfer. We build on this base case with a sensitivity analysis of radar performance over a proposed range of constellation and radar system parameters. With this analysis pipeline, we comment on which radar parameters should or should not be changed to minimize synchronization requirements. This analysis technique could be extended or modified to evaluate the timing requirements of other geometries for other future multistatic SAR missions, or other interferometric satellite missions.

Surface Deformation and Change↗

NASA NTRS1994

Recycled galaxies in the colliding system Arp 105

Arp 105 of an infrared luminous starburst spiral being torn apart by a massive elliptical close to the center of a cluster of galaxies. The elliptical has already accreted gasrich objects and may be the precursor of a giant cD galaxy. At the tip of colossal tidal tails that emanate from the spiral we find a blue compact dwarf galacy and an irregular of Magellanic type. We propose that these small galaxies are recycled objects being formed out of the tidal debris from the spiral. In Arp 105 we observe that the collision has caused a marked spatial separation of the cold interstellar gas: more than 90% of the CO emission comes from the central region of the spiral, whereas more than 90% of the observed atomic hydrogen is situated beyond 30 kpc from the center of the spiral.

Duc, P.-A.↗

NASA NTRS1992

IRAS and the Boston University Arecibo Galactic H I Survey: A catalog of cloud properties

The Infrared Astronomy Satellite (IRAS) Galactic Plane Surface Brightness Images were used to identify infrared emission associated with cool, diffuse H I clouds detected by the Boston University-Arecibo Galactic H I Survey. These clouds are associated with galactic star clusters, H II regions, and molecular clouds. Using emission-absorption experiments toward galactic H II regions, we determined the H I properties of cool H I clouds seen in absorption against the thermal continuum, including their kinematic distances. Correlations were then made between IRAS sources and these H II regions, thus some of the spatial confusion associated with the IRAS fields near the galactic plane was resolved since the distances to these sources was known. Because we can also correlate the BU-Arecibo clouds with existing CO surveys, these results will allow us to determine the intrinsic properties of the gas (neutral and ionized atomic as well as molecular) and dust for interstellar clouds in the inner galaxy. For the IRAS-identified H II region sample, we have established the far infrared (FIR) luminosities and galactic distribution of these sources.

Bania, Thomas M.↗

NASA NTRS2023

Far-Infrared Line Emission from the Outer Galaxy Cluster Gy 3–7 With SOFIA/FIFI-LS: Physical Conditions and UV Fields

Context. Far-infrared (FIR) line emission provides key information about the gas cooling and heating due to shocks and UV radiation associated with the early stages of star formation. Gas cooling via FIR lines might, however, depend on metallicity. Aims. We aim to quantify the FIR line emission and determine the spatial distribution of the CO rotational temperature, ultraviolet (UV) radiation field, and H2 number density toward the embedded cluster Gy 3–7 in the CMa–l224 star-forming region, whose metallicity is expected to be intermediate between that of the Large Magellanic Cloud and the Solar neighborhood. By comparing the total luminosities of CO and [O I] toward Gy 3–7 with values found for low- and high-mass protostars extending over a broad range of metallicities, we also aim to identify the possible effects of metallicity on the FIR line cooling within our Galaxy. Methods. We studied SOFIA/FIFI-LS spectra of Gy 3–7, covering several CO transitions from J = 14–13 to 31-30, the OH doublet at 79 µm, the [O I] 63.2 and 145.5 µm, and the [C II] 158 µm lines. The field of view covers a 2 0 × 1 0 region with a resolution of ∼7 00–1800 . Results. The spatial extent of CO high-J (Jup ≥14) emission resembles that of the elongated 160 µm continuum emission detected with Herschel, but its peaks are offset from the positions of the dense cores. The [O I] lines at 63.2 µm and 145.5 µm follow a similar pattern, but their peaks are found closer to the positions of the cores. The CO transitions from J = 14–13 to J = 16–15 are detected throughout the cluster and show a median rotational temperature of 170 ± 30 K on Boltzmann diagrams. Comparisons to other protostars observed with Herschel show a good agreement with intermediate-mass sources in the inner Galaxy. Assuming an origin of the [O I] and high-J CO emission in UV-irradiated C−shocks, we obtained pre-shock H2 number densities of 104–105 cm−3 and UV radiation field strengths of 0.1–10 Habing fields (G0). Conclusions. Far-IR line observations reveal ongoing star formation in Gy 3–7, dominated by intermediate-mass Class 0/I young stellar objects. The ratio of molecular-to-atomic far-IR line emission shows a decreasing trend with bolometric luminosities of the protostars. However, it does not indicate that the low-metallicity has an impact on the line cooling in Gy 3–7.

stars: formation↗

NASA NTRS1997

NASA/University Joint Venture in Space Science (JOVE)

This system has an immense complex of optical knots that extend several galactic diameters to the north and south of the main optical object. These are star forming regions, some of which are the size of small irregular galaxies. It has a nearby companion called the 'seashell' owing to its disturbed appearance. The data had been reduced and images formed; a figure is attached. The high resolution observations show that the atomic hydrogen (HI) encompasses not only the N-S complex of optical knots but it forms an incomplete ring or tail that extends approximately 3 arcmins to the west. The seashell was not detected, and the HI associated with NGC 5291 itself shows a very large velocity range. The formation mechanism for this disturbed and distorted complex is unclear. X-ray emission suggesting ram sweeping is also observed. This author favors an explanation involving an interaction between the two components, NGC 5291 and the seashell. We are witnessing the formation of tidal tails and bridges between the galaxies and the associated ejecta. Ram sweeping occurs as the system moves bodily through the medium of the cluster of galaxies, Abell 3574, to which NGC 5291 et al. belong. There are numerous concentrations of HI, mostly along the N-S star forming complexes which generally coincide with the optical knots; the larger features contain several x109 solar mass, again the magnitude of a small irregular galaxy. Each knot was compared to a set of criteria designed to test if the feature was stable against its own internal kinetic energy, and stable against the tidal forces of the host galaxy. At least one of the objects (Knot B) appears to be a bound system suggesting that it is a genuinely young dwarf irregular galaxy that has evolved from the material associated with his interacting complex. We conclude that we are witnessing the early evolution of young galaxies and that NGC 5291 and the seashell are a nursery.

Gottesman, Stephen T.↗

NASA NTRS1994

Interstellar gas and dust in the young cluster IC 348

We have completed a multiband absorption- and emission-line study of a star embedded in the young cluster IC 348, to determine the environmental effect of star formation on the interstellar medium (ISM) local to the region. The hottest and youngest star in IC 348 is BD +31 deg 643, a B5 V star which samples the inner bright nebular region. The nearby star omicron Per, which lies only 8 min to the north and is thought to lie beyond IC 348, samples the gas and dust which has not been processed by very recent star formation. We speculate that the ISM throughout the region was originally the same as that currently seen toward omicron Per, but now the constrasting environmental conditions due to the recent star formation have led to marked differences in the atomic, molecular, and dust characteristics of IC 348. These contrasts include what we have termed a 'composite' UV extinction curve for BD +31 deg 643, evidence for enhanced density and enhanced depletions within IC 348 and very different molecular abundances in the interstellar sightline to BD +31 deg 643. Toward BD +31 deg 643, we find a higher column density of CH, but lower CN and very much higher CH(+) than measured toward omicron Per. We conclude that the physical and chemical state of the gas and dust has been altered by local processes and conditions within IC 348. The characteristics of the ISM in IC 348, via our study of the star BD +31 deg 643, closely resembles those seen toward rho Oph, another sight line passing through a bright nebular region. However, the stars are not as hot in IC 348 as in Ophiuchus, so their effect on the local ISM is not as severe.

Snow, Theodore P.↗

NASA NTRS1999

Interstellar Polycyclic Aromatic Compounds and Astrophysics

Hodgins, Douglas M.↗

NASA NTRS2015

A Data Exploration Tool for Large Sets of Spectra

We present an exploration tool for very large spectrum data sets such as the SDSS (Sloan Digital Sky Survey), LAMOST (Large Sky Area Multi-Object Fiber Spectroscopic Telescope), and 4MOST (4-meter Multi-Object Spectroscopic Telescope) data sets. The tool works in two stages: the first uses batch processing and the second runs interactively. The latter employs the NASA hyperwall, a configuration of 128 workstation displays (8 by 16 array) controlled by a parallelized software suite running on NASA's Pleiades supercomputer. The stellar subset of the Sloan Digital Sky Survey, DR10, was chosen to show how the our tool may be used. In stage one, SDSS files for 569,740 stars are processed through our data pipeline. The pipeline fits each spectrum using an iterative continuum algorithm, distinguishing emission from absorption and handling molecular absorption bands correctly. It then measures 1659 discrete atomic and molecular spectral features that were carefully preselected based on their likelihood of being visible at some spectral type. The depths relative to the local continuum at each feature wavelength are determined for each spectrum: these depths, the local S/N (signal to noise ratio) level, and DR10-supplied variables such as magnitudes, colors, positions, and radial velocities are the basic measured quantities used on the hyperwall. In stage two, each hyperwall panel is used to display a 2-D scatter plot showing the depth of feature A vs the depth of feature B for all of the stars. A and B change from panel to panel. The relationships between the various (A,B) strengths and any distinctive clustering are immediately apparent when examining and inter-comparing the different panels on the hyperwall. The interactive software allows the user to select the stars in any interesting region of any 2-D plot on the hyperwall, immediately rendering the same stars on all the other 2-D plots in a unique color. The process may be repeated multiple times, each selection displaying a distinctive color on all the plots. At any time, the spectra of the selected stars may be examined in detail on a connected workstation display. We illustrate how our approach allows us to quickly isolate and examine such interesting stellar subsets as EMP (Extremely Metal‐Poor) stars, CV (Cataclymic Variable) stars and C (Carbon)-rich stars.

Data Exploration↗

NASA NTRS1995

A Coupled-Cluster Study of the Molecular Structure, Vibrational Spectrum, and Heats of Formation of XONO2 (X=H, F, Cl)

The equilibrium structures, harmonic vibrational frequencies, dipole moments, and IR intensities of nitric acid, fluorine nitrate, and chlorine nitrate have been investigated by using the singles and doubles coupled cluster method that also includes a perturbational estimate of the effects of connected triple excitations, CCSD(T). A standard triple-zeta double-polarized basis set was utilized. The equilibrium geometries and vibrational spectra of HONO2 and ClONO2 are shown to be in excellent agreement with the available experimental data. The ab initio vibrational spectrum of FONO2 is also shown to be in excellent agreement with experiment. Unlike the FOOF and FON molecules, but similar to the cis- and trans-FONO molecules, FONO2 is shown to possess normal bond distances. The bonding in FONO2 is shown to be more similar to that in ClONO2 than that in HONO2, although there are still significant differences, especially in the partial atomic charges as deduced from Mulliken populations. This causes FONO2 to possess almost no dipole moment, which is very different to both HONO2 and ClONO2. By using large atomic natural orbital basis sets, CCSD(T) energies are computed for four isodesmic reactions in order to determine an accurate heat of formation for FONO2. Our best estimate for DELTA H(raised circle) (sub f,298) is 3.1 plus or minus 2.0 kcal/mol, indicating that the F-ONO2 bond energy is 31.3 kcal/mol.

Lee, Timothy J.↗

NASA NTRS1996

The Global File System

The global file system (GFS) is a prototype design for a distributed file system in which cluster nodes physically share storage devices connected via a network-like fiber channel. Networks and network-attached storage devices have advanced to a level of performance and extensibility so that the previous disadvantages of shared disk architectures are no longer valid. This shared storage architecture attempts to exploit the sophistication of storage device technologies whereas a server architecture diminishes a device's role to that of a simple component. GFS distributes the file system responsibilities across processing nodes, storage across the devices, and file system resources across the entire storage pool. GFS caches data on the storage devices instead of the main memories of the machines. Consistency is established by using a locking mechanism maintained by the storage devices to facilitate atomic read-modify-write operations. The locking mechanism is being prototyped in the Silicon Graphics IRIX operating system and is accessed using standard Unix commands and modules.

Soltis, Steven R.↗

NASA NTRS2000

Laboratory Astrophysics: The Universe in the Palm of Your Hand

Polycyclic aromatic compounds (PACs), a class of organic molecules whose structures are characterized by the presence of two or more fused aromatic rings, have been the subject of astrophysical interest for nearly two decades. Large by interstellar standards (from as few as 20 to perhaps as many as several hundred atoms), it has been suggested that these species are among the most abundant interstellar molecules impacting a wide range of astrophysical phenomena including: (1) the ubiquitous family of infrared emission bands observed in an ever-increasing assortment of astronomical objects; (2) the subtle but rich array of discrete visible/near-infrared interstellar molecular absorption features known as the diffuse interstellar bands (DIBs); (3) the broad near-infrared quasi-continuum observed in a number of nebulae known as excess red emission (ERE); (4) the interstellar ultraviolet extinction curve and broad '2200 Angstrom bump'; and (5) the heating/cooling mechanisms of interstellar clouds. Nevertheless, until recently a lack of good-quality laboratory spectroscopic data on PACs under astrophysically relevant conditions (i.e. isolated, ionized molecules, ionized molecular clusters, etc.) has hindered critical evaluation and extension of this model. Fortunately, the last decade has seen an explosion of experimental and theoretical techniques aimed specifically at addressing these issues. Indeed, many of these techniques will be explored in the series of talks which constitute this forum. This talk will provide an overview of the studies of the spectroscopic properties of isolated, neutral, and ionized PACs that have been conducted in the Astrochemistry Laboratory at NASA Ames, together with a consideration of their implications for astrophysics. Particular attention will be paid to models of the interstellar infrared emission spectra generated using the available database of laboratory PAC infrared spectra and the natural ability of this database to accommodate the variations observed in the astronomical spectra. Such models provide insight into the structure, abundance, and ionization state of the interstellar PAC population and, in turn, provide direct insight into the processes of carbon nucleation, growth and evolution as matter is processed through the interstellar medium. These models will be followed by a more in depth look at some specific aspects of the interstellar infrared emission spectrum, considering both what we can learn about them and what we can learn from them. Finally, some of the limitations of the current model and the available spectroscopic dataset will be 'dered along with future experimental directions designed to address these shortcomings. Further information about this and the related areas of research currently ongoing in the Astrochemistry Laboratory can be found at our world wide web site. http://www-space.arc.nasa.gov/(tilda)astrochem

Hudgins, Douglas M.↗

NASA NTRS1993

Theoretical research program to study chemical reactions in AOTV bow shock tubes

The main focus was the development, implementation, and calibration of methods for performing molecular electronic structure calculations to high accuracy. These various methods were then applied to a number of chemical reactions and species of interest to NASA, notably in the area of combustion chemistry. Among the development work undertaken was a collaborative effort to develop a program to efficiently predict molecular structures and vibrational frequencies using energy derivatives. Another major development effort involved the design of new atomic basis sets for use in chemical studies: these sets were considerably more accurate than those previously in use. Much effort was also devoted to calibrating methods for computing accurate molecular wave functions, including the first reliable calibrations for realistic molecules using full CI results. A wide variety of application calculations were undertaken. One area of interest was the spectroscopy and thermochemistry of small molecules, including establishing small molecule binding energies to an accuracy rivaling, or even on occasion surpassing, the experiment. Such binding energies are essential input to modeling chemical reaction processes, such as combustion. Studies of large molecules and processes important in both hydrogen and hydrocarbon combustion chemistry were also carried out. Finally, some effort was devoted to the structure and spectroscopy of small metal clusters, with applications to materials science problems.

Taylor, Peter R.↗

NASA NTRS1995

The Ozonide Anion: A Theoretical Study

Complete active space self-consistent field (CASSCF) and CASSCF second order perturbation theory (CASPT2) methods have been used for the geometry optimization and calculation of harmonic and fundamental frequencies of the ozonide ion O3(-) and the ozonide lithium complex Li(+)O3(-). For O3(-) harmonic frequencies have also been obtained using the coupled-cluster method, CCSD(T). Infrared intensities are computed from dipole moment derivatives at the CASSCF level. The predicted equilibrium geometry for O3(-) is: Roo = 1.361 Angstroms and angle ooo = 115.4 degrees, and the fundamental frequencies are: nu(sub 1) = 989 per centimeter, nu(sub 2) 556 per centimeter, nu(sub 3) = 870 per centimeter (experimental values are: Roo =1.36 plus or minus 0.02 Angstroms, angle (ooo) = 111.8 plus or minus 2.0 degrees, nu(sub 1) = 975(50) per centimeter, nu(sub 2) = 550(50) per centimeter, nu(sub 3) = 880(50) per centimeter). Corresponding data for the lithium ozonide complex have also been obtained. The presented data contradict the previous interpretation of the IR and Raman spectrum obtained after deposition of ozone in N2, argon, or neon matrices with atomic beams of alkali metals. The presence of the lithium cation raises the asymmetric stretch frequency to about 940 per centimeter, which is contradictory to assumptions made in the assignments of the matrix spectra. Calculations made in a dielectric medium strongly suggest that the effect of the matrix on the IR spectrum is small for O3(-) itself. The dissociation and atomization energies of O3(-) are found to be in agreement with experiment.

Borowski, Poitr↗

NASA NTRS1993

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Thompson, David W.↗