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At least 541 records · Page 30

Polyimides from a methylene-bridged dianhydride

High-molecular weight, high-temperature, highly optically transparent films suitable for electronic and aerospace applications were prepared based on a novel methylene-bridged dianhydride 3,3-prime bis(3,4-dicarboxyphenoxy) diphenylmethane dianhydride (PDMDA). All films had lower dielectric constants and significantly higher optical transparency than the commercial Kapton H film, with air-cured films having slightly higher dielectric constants and lower optical transparency than vacuum films, due to oxidative cross-linking.

Boston, Harold G.↗

Variability of (O I) 6300-A emission near Io

Observations of (O I) 6300-A emission near Io have been obtained in 1990, 1991, and 1992 by the National Solar Observatory staff using the solar-stellar spectrography on the McMath-Pierce telescope at Kitt Peak. High-resolution spectra with a resolving power of about 1.2 x 10(exp 5) were obtained with an integration time of 10-15 min each. The viewing aperture for the observations was 5.2 arc sec x 5.2 arc sec centered on Io, with spatial resolution limited within this area by seeing conditions. Observations thus far have been reduced to obtain average brightness values over the aperture which range from approximately 200 to 1000 R for a number of different Io phase angles and Io system III longitudes. The (O I) 6300-A emission brightness exhibits an east-west asymmetry, where the average intensity for Io phase angles in the west (receding ansa) is 1.5 times brighter than in the east (approaching ansa). Similar east-west intensity ratios have also been observed for neutrals near Io and ions in the plasma torus for a number of other optical and ultraviolet emission lines which are excited by electron impact. In addition to the east-west asymmetry, the (O I) 6300-A emission brightness exhibits a strong dependence on the Io system III longitude angle, with a maximum value occurring in the range 200 deg +/- 50 deg. Earlier IUE observations of ultraviolet emission lines of O and S near Io obtained over a number of years have measured the east-west asymmetry, but the long IUE integration times of approximately 7-14 hours masked any detection of system III variability. For the (O I) 6300-A emission, the O(1D) state may be excited by electron impact of atomic oxygen and by electron impact dissociation of SO. The molecule SO may be present at the exobase or may be produced above the exobase as the dominant product of SO2 dissociation by electron impact. Preliminary assessment indicates that production of O(1D) by molecular dissociation may be more important. The (O I) 6300-A emission may therefore provide a remote signature for monitoring (1) the upward transport rates of molecular species in Io's atmosphere, (2) the relative abundance and time-variable dissociation of SO2 and/or SO at the exobase and in the corona of Io, and (3) the spatial distribution of these escaping molecular and atomic species and their ion production rates in the planetary magnetosphere.

Scherb, F.↗

Data Base for CFD Validation

The flow behind the shock wave formed around objects which fly at hypervelocity behaves differently from that of a perfect gas. Molecules become vibrationally excited, dissociated, and ionized. The hot gas may emit or absorb radiation. When the atoms produced by dissociation reach the wall surface, chemical reactions, including recombination, may occur. The thermochemical phenomena of vibration, dissociation, ionization, surface chemical reaction, and radiation are referred to commonly as high-temperature real-gas phenomena. The phenomena cause changes in the dynamic behavior of the flow and the surface pressure and heat transfer distribution around the object. The character of a real gas is described by the internal degrees of freedom and state of constituent molecules; nitrogen and oxygen for air. The internal energy states, rotation, vibration and electronic, of the molecules are excited and, in the limit, the molecular bonds are exceeded and the gas dissociated into atomic and, possibly, ionic constituents. The process of energy transfer causing excitation, dissociation and recombination is a rate process controlled by particle collisions. Binary, two-body, collisions are sufficient to cause internal excitation, dissociation and ionization while three-body collisions are required to recombine the particles into molecular constituents. If the rates of energy transfer are fast with respect to the local fluid dynamic time scale the gas is in, or nearly in, equilibrium. If the energy transfer rates are very slow the gas can be described as frozen. In all other instances, wherein any of the energy exchange rates are comparable to the local fluid time scale, the gas will be thermally or chemically reacting and out of equilibrium. Real gas thermochemical nonequilibrium processes are important in the determination of aerodynamic heating; both convective (including wall catalytic effects) and radiative heating. To illustrate this we consider the hypervelocity flow over a bluff body typical of an atmospheric entry vehicle or an aerospace transfer vehicle (ASTV). The qualitative aspects of a hypersonic flow field over a bluff body are discussed in two parts, forebody and afterbody, with attention to which particular physical effects must be included in an analysis. This will indicate what type of numerical modeling will be adequate in each region of the flow. A bluff forebody flow field is dominated by the presence of the strong bow shock wave and the consequent heating, and chemical reaction of the gas. At high altitude hypersonic flight conditions the thermal excitation and chemical reaction of the gas occur slowly enough that a significant portion of the flow field is in a state of thermochemical nonequilibrium. A second important effect is the presence of the thick boundary layer along the forebody surface. In this region there are large thermal and chemical species gradients due to the interaction of the gas with the wall. Also at high altitudes the shock wave and the boundary layer may become so thick that they merge; in this case the entire shock layer is dominated by viscous effects.

Deiwert, George S.↗

Achieving Chemical Accuracy with Coupled-Cluster Theory

Due to formal and computational advances in coupled-cluster theory over the past few years, it is now possible to obtain very accurate molecular geometries, vibrational frequencies, heats of formation, binding energies, and vertical electronic excitation energies. The present monograph reviews the advances that have lead to the current state-of-the art, and also summarizes selected examples from the published literature.

Lee, Timothy J.↗

A Binary-Encounter-Bethe Approach to Simulate DNA Damage by the Direct Effect

The DNA damage is of crucial importance in the understanding of the effects of ionizing radiation. The main mechanisms of DNA damage are by the direct effect of radiation (e.g. direct ionization) and by indirect effect (e.g. damage by.OH radicals created by the radiolysis of water). Despite years of research in this area, many questions on the formation of DNA damage remains. To refine existing DNA damage models, an approach based on the Binary‐Encounter‐Bethe (BEB) model was developed[1]. This model calculates differential cross sections for ionization of the molecular orbitals of the DNA bases, sugars and phosphates using the electron binding energy, the mean kinetic energy and the occupancy number of the orbital. This cross section has an analytic form which is quite convenient to use and allows the sampling of the energy loss occurring during an ionization event. To simulate the radiation track structure, the code RITRACKS developed at the NASA Johnson Space Center is used[2]. This code calculates all the energy deposition events and the formation of the radiolytic species by the ion and the secondary electrons as well. We have also developed a technique to use the integrated BEB cross section for the bases, sugar and phosphates in the radiation transport code RITRACKS. These techniques should allow the simulation of DNA damage by ionizing radiation, and understanding of the formation of double‐strand breaks caused by clustered damage in different conditions.

Plante, Ianik↗

Magnetite as Possible Template for the Synthesis of Chiral Organics in Carbonaceous Chondrites

The main goal of the Japanese Aerospace Ex-ploration Agency (JAXA) Hayabusa-2 mission is to visit and return to Earth samples of a C-type asteroid (162173) 1999 JU3 in order to understand the origin and nature of organic materials in the Solar System. Life on Earth shows preference towards the set of organics with particular spatial arrangements, this 'selectivity' is a crucial criterion for life. With only rare exceptions, life 'determines' to use the left- (L-) form over the right- (D-) form of amino acids, resulting in a L-enantiomeric excess (ee). Recent studies have shown that L-ee is found within the alpha-methyl amino acids in meteorites [1, 2], which are amino acids with rare terrestrial occurrence, and thus point towards a plausible abiotic origin for ee. One of the proposed origins of chiral asymmetry of amino acids in meteorites is their formation with the presence of asymmetric catalysts [3]. The catalytic mineral grains acted as a surface at which nebular gases (CO, H2 and NH3) were allowed to condense and react through Fisher Tropsch type (FTT) syntheses to form the organics observed in meteorites [4]. Magnetite is shown to be an effective catalyst of the synthesis of amino acids that are commonly found in meteorites [5]. It has also taken the form as spiral magnetites (a.k.a. 'plaquettes'), which were found in various carbonaceous chondrites (CCs), including C2s Tagish Lake and Esseibi, CI Orgueil, and CR chondrites [e.g., 6, 7, 8]. In addition, L-ee for amino acids are common in the aqueously altered CCs, as opposed to the unaltered CCs [1]. It seems possible that the synthesis of amino acids with chiral preferences is correlated to the alteration process experienced by the asteroid parent body, and related to the configuration of spiral magnetite catalysts. Since C-type asteroids are considered to be enriched in organic matter, and the spectral data of 1999 JU3 indicates a certain de-gree of aqueous alteration [9], the Hayabusa-2 mission serves as a perfect chance to attest this argument. In order to understand the distribution of spiral magnetites among different meteorite classes, as well as to investigate their spiral configurations and correlation to molecular asymmetry, we observed polished thin sections of CCs using scanning electron microscope (SEM) imaging. Individual magnetite grains were picked, embedded in epoxy, thin-sectioned using an ultra-microtome, and studied with electron backscatter diffraction (EBSD) in order to reconstruct the crystal orientation along the stack of magnetite disks.

Chan, Q. H. S.↗

Fluorine and Lithium at the Kimberley Outcrop, Gale Crater

ChemCam is an active remote sensing instrument which has operated successfully on MSL since landing in August, 2012. Its laser pulses remove dust and to profile through weathering coatings of rocks up to 7 m away. Laser-induced breakdown spectroscopy (LIBS) produces emission spectra of materials ablated from the samples in electronically excited states. As the plasma cools, elements can recombine and molecular emission lines are observed. Recent experiments have shown that some of these molecular emissions can be much brighter than the associated atomic lines, especially when halo-gens and rare earth elements are present. We observed these molecular emissions in some of the ChemCam spectra and report the first detection of chlorine and fluorine with ChemCam. It is also the first time ever that fluorine has been detected on the surface of Mars. Among all the F-bearing observations, one third are observed in the Kimberley outcrop. We will dis-cuss the potential mineralogies related to these observations as well as the related elemental correlations and propose interpretations.

Forni, O.↗

Equation of state and phase diagram of dense hydrogen

The equation of state of hydrogen was calculated for specific volumes ranging from 0.01 to 0.0001 cm3/mole and for temperatures ranging from 200 to 1 million K. Three phases are considered: the molecular solid, the metallic solid and the fluid. Chemical equilibrium between molecules, atoms, ions and electrons is considered in calculating the properties of the fluid phase. Transitions between the three phases will be discussed. The triple point, where the three phases coexist, is calculated to occur at 2.3 Mbar and 1679 K. At higher temperatures and pressures, the molecular solid is unstable.

Kerley, G. I.↗

Analytic evaluation of two-center molecular integrals

By using the Fourier-transform technique, the explicit expressions for the one-electron - two-center overlap integrals of Slater-type atomic orbitals up to 3d are derived. The final expressions are analytic, simple, and independent of local coordinates. Furthermore, they do not contain the nonclosed-form of exponential integrals which were presented in expressions given in earlier work. It is shown that the two-electron - two-center Coulomb integrals, as well as the hybrid integrals, can simply be expressed in terms of these integrals. The numerical instability arising from the situation in which the exponents of the two orbitals are almost equal is discussed, and a solution for this problem based on a Taylor-series expansion of the integral is suggested.

Tai, H.↗

Simple ultraviolet calibration source with reference spectra and its use with the Galileo orbiter ultraviolet spectrometer

A simple compact electron impact laboratory source of UV radiation has been developed and is used to obtain calibrated optically thin VUV spectra and synthetic spectral models for important molecular band systems of H2, N2, and the n 1P0 Rydberg series of He. The relative spectral intensity of the electron impact source can be used as the primary calibration standard for VUV instrumentation in the 80-230 nm range and with FWHM of not less than 0.4 nm. The accuracy of the present method is 10 percent in the FUV and 20 percent in the EUV. Results for calibration of the Galileo orbiter ultraviolet spectrometer have been compared with those obtained using other methods.

Shemansky, D. E.↗

Three-Stage InP Submillimeter-Wave MMIC Amplifier

A submillimeter-wave monolithic integrated- circuit (S-MMIC) amplifier has been designed and fabricated using an indium phosphide (InP) 35-nm gate-length high electron mobility transistor (HEMT) device, developed at Northrop Grumman Corporation. The HEMT device employs two fingers each 15 micrometers wide. The HEMT wafers are grown by molecular beam epitaxy (MBE) and make use of a pseudomorphic In0.75Ga0.25As channel, a silicon delta-doping layer as the electron supply, an In0.52Al0.48As buffer layer, and an InP substrate. The three-stage design uses coplanar waveguide topology with a very narrow ground-to-ground spacing of 14 micrometers. Quarter-wave matching transmission lines, on-chip metal-insulator-metal shunt capacitors, series thin-film resistors, and matching stubs were used in the design. Series resistors in the shunt branch arm provide the basic circuit stabilization. The S-MMIC amplifier was measured for S-parameters and found to be centered at 320 GHz with 13-15-dB gain from 300-345 GHz. This chip was developed as part of the DARPA Submillimeter Wave Imaging Focal Plane Technology (SWIFT) program (see figure). Submillimeter-wave amplifiers could enable more sensitive receivers for earth science, planetary remote sensing, and astrophysics telescopes, particularly in radio astronomy, both from the ground and in space. A small atmospheric window at 340 GHz exists and could enable ground-based observations. However, the submillimeter-wave regime (above 300 GHz) is best used for space telescopes as Earth s atmosphere attenuates most of the signal through water and oxygen absorption. Future radio telescopes could make use of S-MMIC amplifiers for wideband, low noise, instantaneous frequency coverage, particularly in the case of heterodyne array receivers.

Pukala, David↗

An ab initio benchmark study of the H + CO --> HCO reaction

The H + CO --> HCO reaction has been characterized with correlation consistent basis sets at five levels of theory in order to benchmark the sensitivities of the barrier height and reaction ergicity to the one-electron and n-electron expansions of the electronic wave function. Single and multireference methods are compared and contrasted. The coupled cluster method RCCSD(T) was found to be in very good agreement with Davidson-corrected internally-contracted multireference configuration interaction (MRCI+Q). Second-order Moller-Plesset perturbation theory (MP2) was also employed. The estimated complete basis set (CBS) limits for the barrier height (in kcal/mol) for the five methods, including harmonic zero-point energy corrections, are MP2, 4.66; RCCSD, 4.78; RCCSD(T), 4.15; MRCI, 5.10; and MRCI+Q, 4.07. Similarly, the estimated CBS limits for the ergicity of the reaction are: MP2, -17.99; RCCSD, -13.34; RCCSD(T), -13.79; MRCI, -11.46; and MRCI+Q, -13.70. Additional basis set explorations for the RCCSD(T) method demonstrate that aug-cc-pVTZ sets, even with some functions removed, are sufficient to reproduce the CBS limits to within 0.1-0.3 kcal/mol.

NASA Discipline Exobiology↗

The behavior of the electron density and temperatue at Millstone Hill during the equinox transition study September 1984

The ionospheric electron density and temperature variations is simulated during the equinox transition study in September 1984 and the results are compared with measurements made at Millstone Hill. The agreement between the modeled and measured electron density and temperature for the quiet day (18 September) is very good but there are large differences on the day of the storm (19 September). On the storm day, the measured electron density decreases by a factor of 1.7 over the previous day, while the model density actually increases slightly. The model failure is attributed to an inadequate increase in the ratio of atomic oxygen to molecular neutral densities in the MSIS neutral atmosphere model, for this particular storm. A factor of 3 to 5 increase in the molecular to atomic oxygen density ratio at 300 km is needed to explain the observed decrease in electron density. The effect of vibrationally excited N sub 2 on the electron density were studied and found to be small.

Richards, P. G.↗

The behavior of the electron density and temperature at Millstone Hill during the equinox transition study September 1984

The ionospheric electron density and temperature variations is simulated during the equinox transition study in September 1984 and the results are compared with measurements made at Millstone Hill. The agreement between the modeled and measured electron density and temperature for the quiet day (18 September) is very good but there are large differences on the day of the storm (19 September). On the storm day, the measured electron density decreases by a factor of 1.7 over the previous day, while the model density actually increases slightly. The model failure is attributed to an inadequate increase in the ratio of atomic oxygen to molecular neutral densities in the MSIS neutral atmosphere model, for this particular storm. A factor of 3 to 5 increase in the molecular to atomic oxygen density ratio at 300 km is needed to explain the observed decrease in electron density. The effect of vibrationally excited N sub 2 on the electron density were studied and found to be small.

Richards, P. G.↗

Spectroscopic diagnostics of the formation of auroral arcs

The theory and mechanisms for spectroscopic observations of auroral arcs are examined. The emission rate ratios of various spectroscopic features are used to determine the average energy of the auroral particles, noting that only proton bombardment of the atmosphere can produce the observed emissions of atomic hydrogen, Balmer alpha, and Balmer beta. The atomic hydrogen particles can cause excitation, stripping, or ionization. Differences in subsequent electron observations due to the relative energy levels of the bombardment are described, and the use of the First Negative bands of molecular N ions and the ground configuration transition in singly atomic O for optical emission studies is outlined. The mean energy of the bombarding electron flux can be obtained and may be equalled under certain conditions by the proton flux. Finally, the characteristics of an ideal spectrometer for exploring auroral emissions are introduced.

Rees, M. H.↗

Sounding rocket flight report, MUMP 9 and MUMP 10

The results of the launching of two-Marshall-University of Michigan Probes (MUMP 9 and MUMP 10), Nike-Tomahawk sounding rocket payloads, are summarized. The MUMP is similar to the thermosphere probe, an ejectable instrument package for studying the variability of the earth's atmospheric parameters. The MUMP 9 payload included an omegatron mass analyzer, a molecular fluorescence densitometer, a mini-tilty filter, and a lunar position sensor. This complement of instruments permitted the determination of the molecular nitrogen density and temperature in the altitude range from approximately 143 to 297 km over Wallops Island, Virginia, during January 1971. The MUMP 10 payload included an omegatron mass analyzer, an electron temperature probe, a cryogenic densitometer, and a solar position sensor. These instruments permitted the determination of the molecular nitrogen density and temperature and the charged particle density and temperature in the altitude range from approximately 145 to 290 km over Wallops Island during the afternoon preceding the MUMP 9 launch.

Grassl, H. J.↗

Observations of DCO/plus/ - The electron abundance in dark clouds

The J equals 2-1 rotational line of DCO(plus) has been definitely detected in five molecular clouds, including three dark clouds, L63, L134, and L134 N, and marginally detected in four others. The DCO(plus) emission has been mapped in L134 N and extends over a region of 3 arcmin. The DCO(plus)/HCO(plus) abundance ratio found at the centers of dark clouds is large and implies a fractional electron abundance of less than one hundred millionth. This low electron density sets constraints on the metals and possibly CO as well as on the hydrogen density.

Guelin, M.↗

Measurements by the plasma diagnostics package on STS-3

A comprehensive set of measurements about the orbiter environment are provided by the plasma diagnostics package (PDP). Ion and electron particle densities, energies, and spatial distribution functions; ion mass for identification of particular molecular ion species; and magnetic fields, electric fields and electromagnetic waves over a broad frequency range are studied. Shuttle environmental measurements will be made both on the pallet and, by use of the remote manipulator system (RMS), the PDP will be maneuvered in and external to the bay area to continue environmental measurements and to carry on a joint plasma experiment with the Utah State University fast-pulsed electron generator. Results of orbiter environment EMI measurements and S-band field strengths as well as preliminary results from wake search operations indicating wake boundary identifiers are reported.

Shawhan, S. D.↗