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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Laser studies of the photodissociation dynamics of cometary radicals

In the past year, it was shown that in the 193 nm photolysis of C2H, the C2 radical is produced in a variety of electronic, vibrational, and rotational states. The relative population of the vibrational and rotational states of C2(A 1 Pi u), C2(B 1 Sigma g +), and C2(A 3 Pi u) were determined in a static gas cell and in a pulsed molecular beam. It seems as though the original angular momentum of the C2H molecule appears as part of the angular momentum of the C2 radical. A attempt is being made to discover the mathematical relationship that governs this mapping. New information about the bond dissociation energy of the C2 radical was produces. C2(b 3 Sigma g -) and C2( 1 Delta g) were detected in the photolysis of C2H via time resolved infrared emission spectroscopy. In the former case, vibrational excitation up to v'' = 4 is observed. All of the results suggest that the C2 models in comets need to consider the presence of vibrationally excited C2 radicals in comets. The laser induced fluorescence spectra of the C3 was observed as a product of the 193 nm photolysis of allene and propyne. The populations of the rotational levels are identical in both cases. This result has led us to conclude that an isomerization reaction occurs in the photolysis of propyne which leads to the same C3H2 intermediate that is formed in the photolysis of C3H4. Since the former molecule is one of the most abundant in the interstellar medium it is also likely that its precursor is also present in comets. This would explain why C3 is observed in comets.

Jackson, William M.↗
NASA NTRS1994

Pressure broadening of vibrational Raman lines in N2 at temperatures below 300 K

Using quasi-cw stimulated Raman gain spectroscopy, the pressure broadening coefficients for the N2 vibrational Q-branch transitions have been measured over the temperature range 113-297 K for the rotational components J = 4, 6, 8, 10, and 12. The experimental results are fit to a simple power law to give an empirical formula for the temperature dependence of the pressure broadening over the 100-300 K range. These results are also compared to previously published scaling laws that are based on collision induced rotational transition rates.

Herring, G. C.↗
NASA NTRSDate not supplied

Ramdb: The NASA Raman Spectral Database (version 1.00).

Given that, in most instances, minimal sample preparation is required and due to its contactless instrument design, Raman spectroscopy is one of the most versatile vibrational spectroscopic techniques for the chemical analysis of environmental and biological specimens. The diversity of applications of Raman spectroscopy ranges anywhere from art [1] to planetary science missions [2]. The advancement in the use of Raman spectroscopy in Solar System missions, notably in post-mission sample return analysis, requires a spectral library holding the broad range of specimens that could be found in Solar System sources. For this purpose, we have initiated the development of a Raman spectral database (Ramdb) at NASA Ames Research Center. Currently, the database includes experimental and theoretical Raman spectra of PAHs [3, 4], as well as laboratory Raman spectra of amino acids, carbon allotropes, minerals, and analogs relevance to Earth Sciences [5], Exobiology [6], Planetary [7], and Astrochemistry [8] to name just a few examples. Ramdb can be found on the web at www.astrochemistry.org/ramdb, where raw and processed Raman spectra can be downloaded in CSV format. The laboratory Raman spectra are measured using a laser Raman spectrometer (JASCO NRS-5500-532QRI). The Raman instrument is equipped with three excitation lasers, with wavelengths of 405, 532, and 785 nm. A clean silicon substrate is used as the internal standard for wavenumber calibration. Powdered samples were prepared (microscopic >10 um, grounded microscopic < 10 um) on glass slides. Some raw data exhibited a background signal arising as a combination of laser-induced fluorescence from the sample. To correct this background, we developed a Python pipeline that uses open-source Python libraries. Ramdb provides both raw and processed (using Python pipeline) data, which includes tabulated Raman shift transitions and other measurement details. The theoretical Raman band positions of PAHs (pyrene monomers and tetramer clusters) were computed using density functional theory (DFT) with the help of the Gaussian 16 suite of programs [9]. In the near future, Ramdb will serve as a repository of Raman spectral data from Laboratory Astrophysics and Planetary Science experiments involving the irradiation of organic compounds under simulated space and planetary conditions. In addition, online and offline tools will be developed for utilising the database for comparison to the user’s sample.

N Punnakayathil↗
NASA NTRS1984

Origin of the coverage-dependent vibrational shift for O on Ni(100)

The p(2 x 2) and c(2 x 2) coverages of O on Ni(100) are studied with a cluster model. The p(2 x 2) coverge is modeled by the addition of a single O at a fourfold site. The c(2 x 2) is modeled by the explicit inclusion of four additional O atoms. Consistent with electron-energy-loss spectroscopy results, the O-Ni vibration is 85/cm lower for the c(2 x 2) cluster than for the p(2 x 2). The height of O above the surface is 11 pm smaller for the c(2 x 2) coverage. The nature of the O-to-Ni bonding is similar for both coverages.

Bauschlicher, C. W., Jr.↗
NASA NTRS1992

Analysis of the upper atmosphere CO2(nu-2) vibrational temperatures retrieved from ATMOS/Spacelab 3 observations

An analysis of the upper atmospheric (80-116 km) CO2(nu-2) vibrational temperatures retrieved from atmospheric trace molecule spectroscopy (ATMOS) experiment Spacelab 3 spectra by using a nonlocal thermodynamic equilibrium (non-LTE) radiative transfer model is presented. Thermal collisions with atmospheric atomic oxygen keep this vibrational state very close to LTE up to around 100 km. Above this height, the different deviations from LTE retrieved from ATMOS/Spacelab 3 spectra for the Northern and the Southern Hemispheres are explained in terms of this collisional process and in terms of the different kinetic temperature profiles measured at those locations. From these simultaneous observations of the kinetic and CO2(nu-2) vibrational temperatures, a deactivation rate of CO2(nu-2) by O(3P) has been derived which leads to a rate coefficient value between 3 and 6 x 10 exp -12 cu cm/s and favors an independent or negative temperature dependence rate constant for the atmospheric temperature range. Cooling rates induced by the CO2 15-micron fundamental band in the upper mesosphere and lower thermosphere were derived from the simultaneous kinetic temperature, CO2(nu-2) vibrational temperature, and CO2 concentration, as measured by ATMOS/Spacelab 3, and found to be a factor of between 5 and 10 times larger than those generally accepted until very recently.

Lopez-Puertas, M.↗
NASA NTRS1993

Non-invasive optical detection of glucose in cell culture nutrient medium

The objective of the proposed research was to begin the development of a non-invasive optical sensor for measuring glucose concentration in the output medium of cell cultures grown in a unique NASA bioreactor referred to as an integrated rotating-wall vessel (IRWV). The input, a bovine serum based nutrient media, has a known glucose concentration. The cells within the bioreactor digest a portion of the glucose. Thus, the non-invasive optical sensor is needed to monitor the decrease in glucose due to cellular consumption since the critical parameters for sustained cellular productivity are glucose and pH. Previous glucose sensing techniques have used chemical reactions to quantify the glucose concentration. Chemical reactions, however, cannot provide for continuous, real time, non-invasive measurement as is required in this application. Our effort while in the fellowship program was focused on the design, optical setup, and testing of one bench top prototype non-invasive optical sensor using a mid-infrared absorption spectroscopy technique. Glucose has a fundamental vibrational absorption peak in the mid-infrared wavelength range at 9.6 micron. Preliminary absorption data using a CO2 laser were collected at this wavelength for water based glucose solutions at different concentrations and one bovine serum based nutrient medium (GTSF) with added glucose. The results showed near linear absorption responses for the glucose-in-water data with resolutions as high at 108 mg/dl and as low as 10 mg/dl. The nutrient medium had a resolution of 291 mg/dl. The variability of the results was due mainly to thermal and polarization drifts of the laser while the decrease in sensitivity to glucose in the nutrient medium was expected due to the increase in the number of confounders present in the nutrient medium. A multispectral approach needs to be used to compensate for these confounders. The CO2 laser used for these studies was wavelength tunable (9.2 to 10.8 micrometers), however, it was to unstable across wavelengths to test the multispectral approach. From this research, further NASA support was obtained to continue the work throughout the year in which a more stable light source will be used at smaller, near-infrared, wavelengths. It is anticipated that a more compact, non-invasive, optical glucose sensor will be realized which can be used with a bioreactor on future space shuttle missions. It is also anticipated that a multispectral optical sensor may be used to determine the concentration of other molecules needed within the NASA bioreactor, such as fructose and galactose.

Cote, Gerald L.↗
NASA NTRS1992

Density measurements in an expanding flow using holographic interferometry

A nonequilibrium expansion of nitrogen through a 2-dimensional nozzle of a reflected shock tunnel is investigated with laser holography, time resolved pressure measurements and emission spectroscopy to characterize the flow field for vibrational relaxation measurements. A 2D computation is used to simulate the nozzle flow field. Synthetic holograms are generated using the computed density profiles and are compared with the experimental holograms. Also, using a quasi 1-D approximation, populations for each vibrational level are computed by (1) solving the master equations and (2) using the Landau-Teller formulation. Computational accuracy of both models is assessed against the experimental data.

Sharma, Surendra P.↗
NASA NTRS1996

Infrared laser spectroscopy of jet-cooled carbon clusters: the nu 5 band of linear C9

The nu 5 antisymmetric stretching vibration of 1 sigma+g C9 has been observed using direct infrared diode laser absorption spectroscopy of a pulsed supersonic cluster beam. Twenty-eight rovibrational transitions measured in the region of 2079-2081 cm-1 were assigned to this band. A combined least squares fit of these transitions with previously reported nu 6 transitions yielded the following molecular constants for the nu 5 band: nu 0 = 2 079.673 58(17) cm-1, B"= 0.014 321 4(10) cm-1, and B'=0.014 288 9(10) cm-1. The IR intensity of the nu 5 band relative to nu 6 was found to be 0.108 +/- 0.006. Theoretical predictions for the relative intensities vary widely depending upon the level of theory employed, and the experimental value reported here is in reasonable agreement only with the result obtained from the most sophisticated ab initio calculation considered (CCSD).

Non-NASA Center↗
NASA NTRS1977

The vibrational energy levels and dissociation energy of O2/+/ /X 2 Pi g/

The absolute vibrational energy levels of the X 2 Pi g state of O2(+) have been determined by the method of photoelectron spectroscopy in the range nu = 0-25. The precision of the method is comparable to that of conventional high resolution optical spectroscopy. The dissociation energy obtained by a linear extrapolation of the vibrational separations is found to be 6.67 plus or minus 0.18 eV.

Samson, J. A. R.↗
NASA NTRS2003

In-SITU Raman Spectroscopy of Single Microparticle Li-Intercalation Electrodes

Modifications in the vibrational properties of a single microparticle of LiMn2O4 induced by extraction and subsequent injection of Li(+) into the lattice have been monitored in situ via simultaneous acquisition of Raman scattering spectra and cyclic voltammetry data in 1M LiC1O4 solutions in ethylene carbonate (EC):diethyl carbonate (DEC) mixtures (1:1 by volume). Statistical analyses of the spectra in the range 15 < SOD < 45%, where SOD represents the state of discharge (in percent) of the nominally fully charged material, i.e. lambda-MnO2, were found to be consistent with the coexistence of two distinct phases of lithiated metal oxide in agreement with information derived from in situ X-ray diffraction (XRD) measurements involving more conventional battery-type electrodes.

Dokko, Kaoru↗
NASA NTRS1994

Measurement of pressure-broadening and lineshift coefficients at 77 and 296 K of methane lines in the 727 nm band using intracavity laser spectroscopy

Pressure-broadening coefficients and pressure-induced lineshifts of several rotational-vibrational lines have been measured in the 727 nm absorption band of methane at temperatures of 77 and 296 K, using nitrogen, hydrogen, and helium as the foreign-gas collision partners. A technique involving intracavity laser spectroscopy is used to record the methane spectra. Average values of the broadening coefficients (/cm/atm) at 77 K are: 0.199, 0.139, 0.055, and 0.29 for collision partners N2, H2, He, and CH4, respectively. Typical average values of the pressure-induced lineshifts (/cm/atm) at 77 K and for the range of foreign gas pressures between 10 and 200 torr are -0.052 for N2, -0.063 for H2, and +0.031 for He. All the values obtained at 296 K are considerably different from the corresponding values at 77 K. This represents the first report of pressure-broadening and shifting coefficients for the methane transitions in a region where the delta nu(sub C-H) = 5 band occurs.

Singh, Kuldip↗
NASA NTRS1983

Inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of oxide layers in a metal-insulator-metal tunnel junction. The technique involves studying the effects of adsorbed molecules on the tunneling spectrum of such junctions. The data give useful information about the structure, bonding, and orientation of adsorbed molecules. One of the major advantages of inelastic electron tunneling spectroscopy is its sensitivity. It is capable of detecting on the order of 10 to the 10th molecules (a fraction of a monolayer) on a 1 sq mm junction. It has been successfully used in studies of catalysis, biology, trace impurity detection, and electronic excitations. Because of its high sensitivity, this technique shows great promise in the area of solid-state electronic chemical sensing.

Khanna, S. K.↗
NASA NTRS2015

Nonequilibrium Supersonic Freestream Studied Using Coherent Anti-Stokes Raman Spectroscopy

Measurements were conducted at the University of Virginia Supersonic Combustion Facility of the flow in a constant-area duct downstream of a Mach 2 nozzle. The airflow was heated to approximately 1200 K in the facility heater upstream of the nozzle. Dual-pump coherent anti-Stokes Raman spectroscopy was used to measure the rotational and vibrational temperatures of N2 and O2 at two planes in the duct. The expectation was that the vibrational temperature would be in equilibrium, because most scramjet facilities are vitiated air facilities and are in vibrational equilibrium. However, with a flow of clean air, the vibrational temperature of N2 along a streamline remains approximately constant between the measurement plane and the facility heater, the vibrational temperature of O2 in the duct is about 1000 K, and the rotational temperature is consistent with the isentropic flow. The measurements of N2 vibrational temperature enabled cross-stream nonuniformities in the temperature exiting the facility heater to be documented. The measurements are in agreement with computational fluid dynamics models employing separate lumped vibrational and translational/rotational temperatures. Measurements and computations are also reported for a few percent steam addition to the air. The effect of the steam is to bring the flow to thermal equilibrium, also in agreement with the computational fluid dynamics.

Cutler, Andrew D.↗
NASA NTRS2005

Simultaneous Conoscopic Holography and Raman Spectroscopy

A new instrument was developed for chemical characterization of surfaces that combines the analytical power of Raman spectroscopy with the three-dimensional topographic information provided by conoscopic holography. The figure schematically depicts the proposed hybrid instrument. The output of the conoscopic holographic portion of the instrument is a topographical map of the surface; the output of the Raman portion of the instrument is hyperspectral Raman data, from which the chemical and/or biological composition of the surface would be deduced. By virtue of the basic principles of design and operation of the instrument, the hyperspectral image data would be inherently spatially registered with the topographical data. In conoscopic holography, the object and reference beams of classical holography are replaced by the ordinary and extraordinary components generated by a single beam traveling through a birefringent, uniaxial crystal. In the basic conoscopic configuration, a laser light is projected onto a specimen and the resulting illuminated spot becomes a point source of diffuse light that propagates in every direction. The laser beam is rasterscanned in two dimensions (x and y) perpendicular to the beam axis (z), and at each x,y location, the pattern of interference between the ordinary and extraordinary rays is recorded. The recorded interferogram constitutes the conoscopic hologram. Of particular significance for the proposed instrument is that the conoscopic hologram contains information on the z coordinate (height) of the illuminated surface spot. Hence, a topographical map of the specimen is constructed point-by-point by rastering the laser beam in the x and y directions and correlating the x and y coordinates with the z information obtained from the interferograms. Conoscopic imaging is an established method, and conoscopic laboratory instruments for surface metrology are commercially available. In Raman spectroscopy of a surface, one measures the spectrum of laser light scattered inelastically from a laser-illuminated spot on the surface. The wavelengths of the inelastically scattered light differ from that of the incident laser beam by amounts that correspond to the energies of molecular vibrations. The resulting vibrational spectrum can be used to identify the molecules. Raman spectroscopy is a standard laboratory technique for identifying mineralogical, biological, and other specific chemical compositions.

Schramm, Harry F.↗
NASA NTRS2012

Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

DiSanti, M. A.↗
NASA NTRS1986

Infrared line intensities of chlorine monoxide

Absolute infrared line intensities of several ClO lines in the rotational-vibrational (1-0) band were measured using infrared heterodyne spectroscopy near 12 microns. A measurement technique using combined ultraviolet absorption and infrared line measurements near 9.5 microns and 12 microns permitted an accurate determination of the column densities of O3 and ClO in the absorption cell and thus improved ClO line intensities. Results indicate ClO line and band intensities approximately 2.4 times lower than previous experimental results. Effects of possible failure of local thermodynamic equilibrium conditions in the absorption cell and the implication of the results for stratospheric ClO measurements in the infrared are discussed.

Kostiuk, T.↗