SEARCH · Search NASA
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The 3-D rotation-vibration band of carbon monoxide was identified in the near-infrared spectrum of Titan. A preliminary mixing ratio of CO/N2 = 0.00006 was determined. This result supports the probable detection of CO2 by Samuelson et al and strengthens possible analogies between the atmosphere of Titan and conditions on the primitive Earth.
The 3-0 rotation-vibration band of carbon monoxide was identified in the near-infrared spectrum of Titan. A preliminary mixing ratio of CO/N2 = 0.00006 was determined. This result supports the probable detection of CO by Samuelson et al and strengthens possible analogies between the atmosphere of Titan and conditions on the primitive earth. Previously announced in STAR as N83-14039
Spectra obtained at a resolving power of 840, for seven protostellar sources in the region of the 4.67-micron fundamental vibrational band of CO, indicate that the deep absorption feature in W33A near 4.61 microns consists of three features which are seen in other sources, but with varying relative strength. UV-irradiation laboratory experiments with 'dirty ice' temperature cycling allow the identification of two of the features cited with solid CO and CO complexed to other molecules. Cyano group-containing molecules have a lower vapor pressure than CO, and can therefore survive in much warmer environments. The formation and location of the CO- and CN-bearing grain mantles and sources of UV irradiation in cold molecular clouds are discussed. Plausible UV light sources can produce the observed cyano group features, but only under conditions in which local heat sources do not cause evaporation of the CO molecules prior to their photoprocessing.
The 0-0 vibrational band of the F1Pi(u)-X1Sigma(+)g electronic system of C2 has been detected with the IUE in the interstellar medium along the line of sight toward X Per. A column density of 3 (+ or - 1) x 10 to the 12th/f(00) per sq cm was derived by a profile fitting method. The lower limit for 0-0 band oscillator strength was determined from a comparison of the upper limits of observations of the A-X and D-X systems, and an excitation temperature of 40 K was also obtained from the profile fitting. A statistical calculation of the level population with radiative pumping shows that the 0-0 band profile corresponds to a range of values for kinetic temperature, density, and near-IR radiation. An upper limit of 50 K for kinetic temperature was determined from the statistical equilibrium analysis.
The feasibility of using Raman spectral scattering signals for measurements of concentration profiles near a crystal interface during growth or dissolution is discussed. With KH2PO4 (KDP) as a test material, optical multichannel analyzer (OMA) detection of a solute Raman vibrational band provided direct quantification of solute concentration with band intensity. The intersection of incident laser and Raman collection optics provided 3-D selective point measurements of the solution concentration field. Unlike many other techniques, the Raman band intensity is not sensitive to the typical temperature variations. Precision calibration of Raman intensity versus KDP concentration with less than 1 pct standard deviation error levels was demonstrated. A fiber optic, which sampled incident laser intensity and coupled it to the OMA, provided a fully synchronized monitor of fluctuations in laser power to correlate with observed Raman signals. With 1 W of laser power at the sample, good data statistics required eight repeated data collections at approximately 2.5 min collection. The accumulated time represents the concentration measurement time at one spatial location. Photomicroscopy documented a 30 micrometer diameter by 200 micrometer of laser Raman scattering region in the solution near the crystal surface. The laser beam was able to approach up to 25 micrometer from the crystal surface. However, a crystal surface reflected intensity contribution was weakly detectable. Nucleated microcrystals were seen in the crystal-growing solution. These microcrystals convect right up to the crystal surface and indicate no quiet diffusion region under normal gravity conditions. Translation of the solution cell with respect to the optics caused systematic intensity errors.
Recent advances in semiconductor laser technology have produced a reliable lightweight device ideally suited for a spacecraft high resolution molecular spectrometer. Lead-salt tunable diode lasers (TDL) emit in several spectral modes, each with a very narrow linewidth of -0.0003/cm. This spectral resolution is much narrower than typical Doppler broadened molecular linewidths in the mid-IR range. Thus it is possible to detect individual rotational lines within the vibrational band and measure their intensity, which can be used to determine gas concentration. The narrow spectral lines of any impurity gas tend to lie between the narrow lines of the gas of interest. This represents a major advantage over the accepted gas chromatograph mass spectrometer (GCMS) technique for measuring gas concentrations and isotope ratios. The careful and extensive gas purification procedures required to remove impurities for reliable GCMS measurements will not be required for an IR laser gas analysis. The infrared laser gas analysis technique is being developed to measure stable isotopic ratios of gases such as CO2, CH4, N2O, and NH3. This will eventually lead to development of instruments capable of in situ istopic measurements on planets such as Mars. The carbon (C-12, C-13) isotope ratio is indicative of the type of carbon fixation mechanisms (e.g., photosynthesis, respiration) in operation on a planet, while the nitrogen (N-14, N-15) isotope ratio can probably be used to date nitrogen-bearing Martian samples. The absorbance ratio of two adjacent lines of CO2 in the 2300/cm (4.3 micron) region of the spectrum was measured. The precision of the measurement is presently better than 1 percent and significant improvement is anticipated as rapid sweep-integration techniques and computer controlled data acquistion capabilities are incorporated.
Atmospheric winds at heights between 25 and 120 km have been retrieved with precisions of 5/ms from the Doppler shifts of atmospheric absorption lines measured from a satellite-borne instrument. Lines of the upsilon 3 CO2 and upsilon 2 H2O rotation-vibration bands caused by gases in the instrument allowed the instrumental frequency scale to be absolutely calibrated so that accurate relative speeds could be obtained. By comparing the positions of both sets of instrumental lines the calibration of the frequency scale was determined to be stable to a precision of less than 2 x 10(-5) cm during the course of each occultation. It was found that the instrumental resolution of 0.015 cm after apodization, the signal to noise ratio of about 100 and stable calibration allowed relative speeds to be determined to a precision of 5 ms or better by using small numbers of absorption lines between 1600 and 3200 cm. Absolute absorption line positions were simultaneously recovered to precisions of 5 x 10(-5) cm or better. The wind speed profiles determined from four sunset occultations and one sunrise occultation show remarkable similarities in the magnitudes and directions of the zonal wind velocities as functions of height. These wind profiles appear to be manifestations of atmospheric tides.
IR spectroscopy data are the bases of the present comparative study of cometary and interstellar dust compositions, allowing the vibrational bands of molecular components to be directly compared at IR wavelengths. Significant organic and silicate band profile differences are noted between comets and molecular clouds' interstellar grains; attention is given to the range of observational efforts, such as the determination of comets' formation temperature from the ortho/para ratio of H2O, which may serve to resolve the question as to whether interstellar dust and ices were the bases for cometary formation without alteration.
A method is described for forming and spectroscopically characterizing cryogenic aerosols formed in a low temperature gas cell. By adjusting the cell pressure, gas composition and flow rate, the size distribution of aerosol particles can be varied over a wide range. The combination of pressure and flow rate determine the residence time of the aerosols in the cell and hence the time available for the particles to grow. FTIR spectroscopy, over the range from 600/cm to 6000/cm, is used to characterize the aerosols. The particle size distribution can be varied so that, at one extreme, the spectra show only absorption features associated with the infrared active vibrational bands and, at the other, they display both absorption and Mie scattering. In the latter case, Mie scattering theory is used to obtain semiquantitative aerosol size distributions, which can be understood in terms of the interplay between nucleation and condensation. In the case of acetylene aerosols, the infrared spectra suggest that the particles exist in the high temperature cubic phase of the solid.
The Molecular Spectroscopy Lab at NASA-Langley has been involved in a long term effort to carefully characterize the infrared spectra of small molecules of atmospheric interest, including methane, water vapor, ozone, and their isotopic counterparts. High resolution gas phase infrared spectra are obtained using both a tunable diode laser system, and the McMath Fourier transform spectrometer at the Kitt Peak Solar Observatory. Spectra are obtained at various pressures and temperatures for pure gas samples, and for samples containing mixtures of the species of interest in nitrogen, oxygen, or air. From these spectra, using a nonlinear least squares fitting technique, spectral parameters of position, intensity, and half-width were determined for varying laboratory conditions that approximate atmospheric conditions experienced in remote sensing situations. These parameters are of interest in theoretical studies of these species, as well as in allowing more accurate interpretation of remote sensing data. The current work involves the analysis of a series of McMath FTIR spectra of ozone broadened by mixing with air, nitrogen, or oxygen. Each spectrum covers the region from 2396 to 4057/cm. Each vibrational band is analyzed by first diving its region into small intervals containing a few well isolated absorption lines of reasonable intensity. Each of these small intervals is fit by multiple iterations of the nonlinear least square program until residuals are minimized to a reasonable value which corresponds to the noise level of the measured spectrum. Intervals for the 3 nu(sub 3) ozone band in the region from 3000 to 3060 wavenumbers are being examined.
FTIR emission/absorption spectroscopy is used to measure the relative intensities of 88 pairs of rovibrational transitions of OH(X2Pi) distributed over 16 vibrational bands. The experimental technique used to obtain the Einstein A ratios is discussed. The dipole moment function which follows from the intensity ratios along with Einstein A coefficients calculated from mu(r) is presented.
Three electronic transitions of CaS are observed in the blue region of the spectrum. The vibrational bands in these transitions span thousands per cm owing to a large change in geometry. Approximately 1000/cm portion of the spectrum containing these bands is recorded at high resolution by dye laser excitation spectroscopy and analyzed. The states all have Omega = 1, and are tentatively labeled G 1Pi, F 1Pi, and f 3Pi 1. Spectroscopic constants are generated for all three upper states and for the X 1Sigma(+) state from a fit to 4340 individual lines. These constants are used to generate potential curves and Franck-Condon factors.
Optical emission has been observed corresponding to vibrational bands in the NH (A 3Pi - X 3Sigma(-)) electronic transition during collisions of 5 eV, ground-state oxygen O(3P) atoms with MgF2 and Ni surfaces continuously exposed to a beam of hydrazine (N2H4). The NH emission intensity is observed to be about five times greater for MgF2 than for Ni. No dependence on temperature was observed for either surface in the range 240 - 340 K, implying that the NH-producing intermediate species is tightly bound. The half-lifetime for desorption of hydrazine from each surface was measured. This was found to be 120 min for the MgF2 surface at 240 K, and less than 20 min for Ni. After exposure, the surface composition was measured using X-ray photoelectron spectroscopy on the exposed and unexposed areas of both targets.
High levels of ab initio theory are used to investigate the equilibrium structures, vibrational spectra, and relative energetics of FNO2, cis-FONO, and trans-FONO isomers. FNO2 is determined to be 36.9 +/- 2.5 kcal/mol (0 K) more stable than cis-FONO, which is more stable than trans-FONO by 2.5 +/- 1.0 kcal/mol (0 K). The molecular structure of cis-FONO is shown to have typical F-O and central O-N single bond distances, indicating that cis-FONO has a structure analogous to HONO. The computed vibrational spectrum of cis-FONO is shown to be consistent with IR matrix isolation experiments, including isotopic shifts. The experimentally deduced structure of FONO is shown to be incorrect because one of the vibrational bands included in the normal coordinate analysis is either a combination band or an overtone.
The strongest absorption lines are in the v sub 2 vibrational band around 1400/cm; several near-coincident line pairs in this region provide max linestrengths of 1.2 x 10 exp -20 sq. cm/(molecule*cm). High Frequency wavelength modulation coupled with sweep integration were used to minimize noise and maintain spectral discrimination. Reduced pressure sampling was performed using supersonic nozzle and an aerodynamic flow cell to minimize residence time and wall losses of radicals. The astigmatic mirror design provides pathlengths up to 200 m in volume of 3 liters with minimal optical interference fringes; longer pathlengths are possible. The detection limit depends on pathlength and minimum fractional absorptions.
The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.
We have observed 4.6 micrometers fundamental band vibrational absorption lines of (12)CO and (13)CO from six optically obscured OH/IR stars. For each star, the velocities of the CO lines increase steadily with increasing excitation potential. The low-excitation lines have velocities similar to the velocity of the blueshifted component of the 18 cm maser lines of OH. The high-excitation lines have velocities near the stellar velocity as determined by the midpoint of the 18 cm OH lines. The relationship between velocity and excitation potential indicates that the CO lines are formed in the circumstellar region in which the outflow of gas from the star is accelerated from rest to nearly its asymptotic velocity. It should be possible to use models of the formation of the CO lines in OH/IR stars to discover the mechanism or mechanisms which accelerate the gas and initiate mass loss.
We have examined the physical and chemical processes which accompany the propagation of a J-type shock through molecular astrophysical gas of density 10(exp 7.5) - 10(exp 12) H nuclei per cu cm. Our study is primarily relevant to the high-density accretion shocks which are associated with the supersonic infall of material during the collapse of a molecular cloud core to form a protostar. We have carried out a general parameter study to determine the characteristic infrared emission spectrum of dense molecular shocks and the extent of grain destruction within such shocks as a function of relevant shock parameters. Accretion shocks with mass accretion rates approximately greater than 10(exp -5) solar masses per y are plausible sources of the CO v = 2-0 vibrational band emission observed in many protostars, at least for sources of moderate CO v = 2-0 luminosity (approximately less than few x 10(exp 23) W). Rovibrational emissions from H2O and OH are also predicted to be luminous in dense molecular accretion shocks. Vaporization is the dominant mechanism of grain destruction within dense molecular shocks, leading to the efficient removal of those grains which are heated to their vaporization temperature by the combined effects of radiative heating, drag heating, and thermal heating by the hot postshock gas. The criteria for grain vaporization are obtained for grains composed of several different materials: metallic iron, silicate, troilite, refractory organic materials, volatile organic materials, and water ice.