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At least 271 records · Page 15

Hydrogen Bonding and Vibrational Spectroscopy: A Theoretical Study

Effects of hydrogen bonding on vibrational spectra are studied for several hydrogen-bonded complexes, in which hydrogen bonding ranges from weak (<5 kcal/mol) to very strong (>25 kcal/mol). The systems studied include complexes of inorganic acids and salts with water and ammonia, as well as complexes of several organic molecules (nitriles and amino acids) with water. Since anharmonic effects are very strong in hydrogen-bonded systems, anharmonic vibrational frequencies and infrared intensities are computed using the correlation-corrected vibrational self-consistent field (CC-VSCF) method with ab initio potential surfaces at the MP2 and CCSD(T) levels. The most common spectral effects induced by hydrogen bonding are red shifts of stretching vibrational frequencies ranging from approx.200/cm to over 2000/cm and significant increases of infrared intensities for those bonds that participate in hydrogen bonding. However, some systems (e.g. nitrile-water complexes) exhibit shifts in the opposite direction (to the blue) upon formation of hydrogen bonds.

Chaban, Galina M.↗

Mars: Compositional variability of ferric/ferrous minerals and polar volatiles from groundbased imaging spectroscopy

In an attempt to further constrain the ferric and ferrous mineralogy of Mars, Bell et al. (1989; 1990) obtained high resolution imaging spectroscopic data of much of the Martian surface in the visible and near-infrared (0.4-1.1 micron) during the 1988 opposition. Preliminary analysis of these data showed further evidence of crystalline hematite absorption features at 0.8-0.9 microns and 0.6-0.7 microns. Additionally, the 0.6-0.7 micron Fe(III) band was shown to vary across the surface, with a substantial correlation with albedo in the region studied. Calibration of this 1988 data set (along with a similar data set obtained during the 1990 opposition) has been ongoing, and some of the most recent results of the analysis of these data using linear spectral mixture modeling are reported.

Bell, James F., III↗

Mid-infrared (5.0-7.0 microns) imaging spectroscopy of the moon from the KAO

A series of 71 mid-infrared images of a small region of the Moon were obtained from the KAO in October, 1993. These images have been assembled into a 5.0 to 7.0 micron image cube that has been calibrated relative to the average spectrum of this region of the Moon at these wavelengths. The data show that clear, detectable spectral differences exist on the Moon in the mid-IR. Some of the spectral differences are correlated with morphologic features such as craters. Specific spectral features near 5.6 and 6.7 microns may be related to the presence of plagioclase or pyroxene.

Bell, James F., III↗

Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy

Thermoset and thermoplastic polyimides have complementary physical and mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. A combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPN) of thermoset LaRC(TM)-RP46 and thermoplastic LaRC(TM)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0:100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical and mechanical properties. As expected, positronium atoms are not formed in these samples. The second lifetime component has been used to infer the positron trap dimensions. The 'free volume' goes through a minimum at a ratio of about 50:50, and this suggests that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples are discussed.

Singh, Jag J.↗

Resin characterization in cured graphite fiber reinforced composites using diffuse reflectance-FTIR

The feasibility of using diffuse reflectance in combination with Fourier transform infrared spectroscopy to obtain information on cured graphite fiber reinforced polymeric matrix resin composites was investigated. Several graphite/epoxy, polysulfone, and polyimide composites exposed to thermal or radiation environments were examined. An experimental polyimide-sulfone adhesive tape was also studied during processing. In each case, significant changes in resin molecular structure was observed due to environmental exposure. These changes in molecular structure were correlated with previously observed changes in material properties providing new insights into material behavior.

Young, P. R.↗

Polarized fluorescence spectroscopy of O2(+)

Polarized fluorescence measurements involving the A 2Pi(u) - X 2Pi(g) and b 4Sigma(g)(-) - a 4Pi(u) transitions in O2(+) following narrow-band photoexcitation of O2/X 3Sigma(g)(-)/ are reported. The analysis, based on the conventional high-J limit, involves deducing the quadrupole alignment factor from which the relative strengths of degenerate photoexcitation channels responsible for the population distribution in the A 2Pi(u) and b 4Sigma(g)(-) states of O2(+) can be estimated. The measured A-channel polarization exhibits pronounced structure which correlates well with the known positions of Rydberg states, whereas the polarization signal in the b channel has broad and less prominent features. Discrepancies between theoretical and measured results can largely be accounted for by additional configuration mixing and autoionization considerations.

Keller, J. W.↗

Ischemia causes muscle fatigue

The purpose of this investigation was to determine whether ischemia, which reduces oxygenation in the extensor carpi radialis (ECR) muscle, causes a reduction in muscle force production. In eight subjects, muscle oxygenation (TO2) of the right ECR was measured noninvasively and continuously using near infrared spectroscopy (NIRS) while muscle twitch force was elicited by transcutaneous electrical stimulation (1 Hz, 0.1 ms). Baseline measurements of blood volume, muscle oxygenation and twitch force were recorded continuously, then a tourniquet on the upper arm was inflated to one of five different pressure levels: 20, 40, 60 mm Hg (randomized order) and diastolic (69 +/- 9.8 mm Hg) and systolic (106 +/- 12.8 mm Hg) blood pressures. Each pressure level was maintained for 3-5 min, and was followed by a recovery period sufficient to allow measurements to return to baseline. For each respective tourniquet pressure level, mean TO2 decreased from resting baseline (100% TO2) to 99 +/- 1.2% (SEM), 96 +/- 1.9%, 93 +/- 2.8%, 90 +/- 2.5%, and 86 +/- 2.7%, and mean twitch force decreased from resting baseline (100% force) to 99 +/- 0.7% (SEM), 96 +/- 2.7%, 93 +/- 3.1%, 88 +/- 3.2%, and 86 +/- 2.6%. Muscle oxygenation and twitch force at 60 mm Hg tourniquet compression and above were significantly lower (P < 0.05) than baseline value. Reduced twitch force was correlated in a dose-dependent manner with reduced muscle oxygenation (r = 0.78, P < 0.001). Although the correlation does not prove causation, the results indicate that ischemia leading to a 7% or greater reduction in muscle oxygenation causes decreased muscle force production in the forearm extensor muscle. Thus, ischemia associated with a modest decline in TO2 causes muscle fatigue.

Non-NASA Center↗

Nuclear Instruments and Methods in Physics Research: Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy - Section B

Thermoset and thermoplastic polyimides have complementary physical/mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. It is expected that a combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPNs) of thermoset LaRC(Trademark)-RP46 and thermoplastic LARC(Trademark)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0: 100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical/mechanical properties. As expected, positronium atoms are not formed in these samples. The second life time component has been used to infer the positron trap dimensions. The "free volume" goes through a minimum at about 50:50 ratio, suggesting that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples have been discussed in this paper.

Singh, Jag J.↗

Theoretical research program to study transition metal trimers and embedded clusters

Small transition metal clusters were studied at a high level of approximation, including all the valence electrons in the calculation and extensive electron correlation, in order to understand the electronic structure of these small metal clusters. By comparison of dimers, trimers, and possibly higher clusters, the information obtained was used to provide insights into the electronic structure of bulk transition metals. Small metal clusters are currently of considerable experimental interest and some information is becomming available both from matrix electron spin resonance studies and from gas phase spectroscopy. Collaboration between theorists and experimentalists is thus expected to be especially profitable at this time since there is some experimental information which can serve to guide the theoretical work.

Walch, S. P.↗

Deuterium hyperfine structure in interstellar C3HD

The deuterium nuclear quadrupole hyperfine structure of the transition 1(10)-1(01) of the ring molecule cyclopropenylidene-d1 (C3HD) has been observed in emission from interstellar molecular clouds. The narrowest linewidths (approximately 7 kHz) so far observed are in the cloud L1498. The derived D coupling constants Xzz = 186.9(1.4) kHz, eta=0.063(18) agree well with correlations based on other molecules.

NASA Program Exobiology↗

The 2-micron polar haze of Jupiter

Model spectra have been constructed for the CH4 lines of the polar regions of Jupiter in such as way as to encompass the hydrogen pressure-induced opacity and haze layers revealed by high-resolution spectroscopy. Comparisons between observation and model spectra indicate that, for optically thin haze models, the polar haze is primarily located between the 70 and 5 mbar pressure levels; for opaque haze models, the top of the haze layers lies in the vicinity of the 15-mbar level. It is concluded that the polar haze is widely distributed over both polar regions and exhibits no strong correlation with auroral activities.

Kim, Sang J.↗

Adhesion of metals to a clean iron surface studied with LEED and Auger emission spectroscopy.

Discussion of the results of adhesion experiments conducted with various metals contacting a clean iron surface. The metals included gold, silver, nickel, platinum, lead, tantalum, aluminum, and cobalt. Some of the metals were examined with oxygen present on their surface as well as in the clean state. The results indicate that, with the various metals contacting iron, the cohesively weaker will adhere and transfer to the cohesively stronger. The chemical activity of the metal also influenced the adhesive forces measured. With oxygen present on the metal surface, the adhesive forces measured could be correlated with the binding energy of the metal to oxygen.

Buckley, D. H.↗

Evidence for Different Accretion Regimes in GRO J1008-57

We present a comprehensive spectral analysis of the BeXRB GRO J1008-57 over a luminosity range of three orders of magnitude using NuSTAR, Suzaku, and RXTE data. We find significant evolution of the spectral parameters with luminosity. In particular, the photon index hardens with increasing luminosity at intermediate luminosities in the range 10(sup 36) to 10 (sup 37) ergs per second. This evolution is stable and repeatedly observed over different outbursts. However, at the extreme ends of the observed luminosity range, we find that the correlation breaks down, with a significance level of at least 3:7sigma. We conclude that these changes indicate transitions to different accretion regimes, which are characterized by different deceleration processes, such as Coulomb or radiation breaking. We compare our observed luminosity levels of these transitions to theoretical predications and discuss the variation of those theoretical luminosity values with fundamental neutron star parameters. Finally, we present detailed spectroscopy of the unique "triple peaked" outburst in 2014/15 which does not fit in the general parameter evolution with luminosity. The pulse profile on the other hand is consistent with what is expected at this luminosity level, arguing against a change in accretion geometry. In summary, GRO J1008-57 is an ideal target to study different accretion regimes due to the well-constrained evolution of its broad-band spectral continuum over several orders of magnitude in luminosity.

Kühnel, Matthias↗

Parametric dependence of ion temperature and electron density in the SUMMA hot-ion plasma using laser light scattering and emission spectroscopy

Hot-ion plasma experiments were conducted in the NASA Lewis SUMMA facility. A steady-state modified Penning discharge was formed by applying a radially inward dc electric field of several kilovolts near the magnetic mirror maxima. Results are reported for a hydrogen plasma covering a wide range in midplane magnetic flux densities from 0.5 to 3.37 T. Input power greater than 45 kW was obtained with water-cooled cathodes. Steady-state plasmas with ion kinetic temperatures from 18 to 830 eV were produced and measured spectroscopically. These ion temperatures were correlated with current, voltage, and magnetic flux density as the independent variables. Electron density measurements were made using an unusually sensitive Thomson scattering apparatus. The measured electron densities range from 2.1 x 10 to the 11th to 6.8 x 10 to the 12th per cu cm.

Snyder, A.↗

Hard x ray/microwave spectroscopy of solar flares

The joint study of hard x ray and microwave observations of solar flares is extremely important because the two complementary ways of viewing the accelerated electrons yield information that cannot be obtained using hard x rays or microwaves alone. The microwaves can provide spatial information lacking in the hard x rays, and the x ray data can give information on the energy distribution of electrons that remove ambiguities in the radio data. A prerequisite for combining the two data-sets, however, is to first understand which range of microwave frequencies correlate best with the hard x rays. This SMM Guest Investigator grant enabled us to combine multi-frequency OVRO data with calibrated hard x ray data to shed light on the relationship between the two emissions. In particular, the questions of which microwave frequencies correspond to which hard x ray energies, and what is the corresponding energy of the electrons that produce both types of emission are investigated.

Gary, Dale E.↗

Developing Atmospheric Retrieval Methods for Direct Imaging Spectroscopy of Gas Giants in Reflected Light I: Methane Abundances and Basic Cloud Properties

Reflected light spectroscopy and photometry of cool, directly imaged extrasolar giant planets are expected to be performed in the next decade by space-based telescopes equipped with optical wavelength coronagraphs and integral field spectrographs, such as the Wide-Field Infrared Survey Telescope (WFIRST). We are developing a new atmospheric retrieval methodology to help assess the science return and inform the instrument design for such future missions, and ultimately interpret the resulting observations. Our retrieval technique employs an albedo model coupled with both a Markov chain Monte Carlo Ensemble Sampler (emcee) and a multimodal nested sampling algorithm (MultiNest) to map the posterior distribution. This combination makes the global evidence calculation more robust for any given model, and highlights possible discrepancies in the likelihood maps. Here we apply this methodology to simulated spectra of cool giant planets. As a proof-of-concept, our current atmospheric model contains 1 or 2 cloud layers, methane as a major absorber, and a H2-He background gas. This 6-to-9 parameter model is appropriate for Jupiter-like planets and can be easily expanded in the future. In addition to deriving the marginal likelihood distribution and confidence intervals for the model parameters, we perform model selection to determine the significance of methane and cloud detection as a function of expected signal-to-noise, in the presence of spectral noise correlations. After internal validation, the method is applied to realistic reflected-light spectra of Jupiter, Saturn, and HD 99492 c, a likely observing target. We find that the presence or absence of clouds and methane can be determined with high accuracy, while parameters uncertainties are model-dependent.

spectroscopy↗

Correlative Analysis of GRBs Detected by Swift and Suzaku- WAM

It is now well known that a complete understanding of the energetics of the prompt phase of gamma-ray bursts (GRBs) requires full knowledge of the spectrum, extending at least as high as the peak energy (Epeak) of the vF(v) spectrum. Since most gamma-ray bursts (GRBs) have Epeak above the energy range (15-150 keV) of the Burst Alert Telescope (BAT) on Swift, a full understanding of the prompt emission from Swift GRBs requires spectral fits over as broad an energy range as possible. This can be completed for bursts which are simultaneously detected by Swift BAT and the Suzaku Wide-band All-Sky Monitor (WAM), which covers the energy range from 50-5000 keV. Between the launch of Suzaku in July 2005 and the end of 2008, there were 44 gamma-ray bursts (GRBs) which triggered both Swift and WAM and an additional 41 bursts which triggered Swift and were detected by WAM, but did not trigger. A joint BAT-WAM team has cross-calibrated the two instruments using GRBs, and we are now able to perform joint fits on these bursts to determine spectral parameters including Epeak. The results of broad spectral fits allows us to understand the distribution of Epeak for Swift bursts and to calibrate Epeak estimators when Epeak is within the BAT energy range. For those bursts with spectroscopic redshifts, we can calculate the isotropic energy and study various correlations between Epeak and other global burst parameters. Here we present the results of joint Swift/BAT-Suzaku/WAM spectral fits for 77 of the bursts jointly detected by the two instruments. We show that the distribution of spectral fit parameters is consistent with distributions from earlier missions and confirm that Swift bursts are consistent with earlier reported relationships between Epeak and isotropic energy. We show through time-resolved spectroscopy that individual burst pulses are also consistent with this relationship.

Krimm, H.A.↗

Martian Atmospheric Methane Plumes from Meteor Shower Infall: A Hypothesis

Methane plumes in the martian atmosphere have been detected using Earth-based spectroscopy, the Planetary Fourier Spectrometer on the ESA Mars Express mission, and the NASA Mars Science Laboratory. The methane's origin remains a mystery, with proposed sources including volcanism, exogenous sources like impacts and interplanetary dust, aqueous alteration of olivine in the presence of carbonaceous material, release from ancient deposits of methane clathrates, and/or biological activity. To date, none of these phenomena have been found to reliably correlate with the detection of methane plumes. An additional source exists, however: meteor showers could generate martian methane via UV pyrolysis of carbon-rich infall material. We find a correlation between the dates of Mars/cometary orbit encounters and detections of methane on Mars. We hypothesize that cometary debris falls onto Mars during these interactions, depositing freshly disaggregated meteor shower material in a regional concentration. The material generates methane via UV photolysis, resulting in a localized "plume" of short-lived methane.

Fries, M.↗