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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Fourier transform spectroscopy of the nu3 band of the N3 radical

The nu3 transitions of N3 radicals produced by HN3-Cl reactions in a multipass cell (effective path length 100 m) are investigated experimentally using a Fourier-transform spectrometer with maximum resolution 0.004/cm. A total of 176 rotation-vibration lines are listed in a table and used, in combination with published data on 240 optical lines (Douglas and Jones, 1965), to determine the nu3 molecular constants. The lower-than-expected value of the nu3 fundamental frequency (1644.6784/cm) is attributed to the vibronic interaction discussed by Kawaguchi et al. (1981).

Brazier, C. R.↗
NASA NTRS1992

Femtosecond resolution of soft mode dynamics in structural phase transitions

The microscopic pathway along which ions or molecules in a crystal move during structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a 'soft' phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO3 and BaTiO3 are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.

Dougherty, Thomas P.↗
NASA NTRS1990

Theoretical study of the spectroscopy of NO(+)

The spectroscopy of the NO(+) molecule has been studied using multireference configuration-interaction calculations. The peak at 21.7 eV in the photoelectron spectrum of NO is assigned to the (2) 3Pi state (c 3Pi) and the vibrational progression centered at 23.1 eV is assigned to the diabatic (3) 1Pi state (B 1Pi). Several additional bound states with binding energies in excess of 1 eV are characterized in the present work. Radiative lifetimes are presented for many of the states.

Partridge, Harry↗
NASA NTRS2002

Deuterated PAHs in Space

The cosmic deuterium to hydrogen (D/H) ratio is of key importance from a cosmological and stellar evolution perspective since deuterium originates from big-bang nucleosynthesis and is destroyed by stellar thermonuclear reactions. Further, from the interstellar perspective, the galactic distribution of deuterium and the D/H ratio among various molecular species also traces interstellar chemical evolution. Over the past few decades, radio observations have enabled the study of a handful of small, deuterated interstellar species. However, the number of deuterated species detected and environments probed are limited, raising issues of selection effects that hamper generalization and applications to other environments. Infrared spectroscopy of the interstellar medium offers a distinct advantage in this regard as the extent of deuteration of entire chemical families, rather than one species, can be probed. These observations require spaceborne telescopes because the molecular vibrations involving D which produce the strongest IR bands fall in spectral regions which are obscured by terrestrial CO2 absorption. Here we report the tentative detection of the C-D stretching vibration from deuterated interstellar polycyclic aromatic hydrocarbons in the Orion nebula. Since the PAH emission features are widespread and probe many different types of cosmic environments, follow up observations of deuterated PAHs will provide fundamental, far reaching new insight and perspective into galactic and extragalactic processes.

Peeters, Els↗
NASA NTRS1998

Near-infrared spectroscopy of the proto-planetary nebula CRL 618 and the origin of the hydrocarbon dust component in the interstellar medium

A new 2.8-3.8 micrometers spectrum of the carbon-rich protoplanetary nebula CRL 618 confirms the previous detection of a circumstellar 3.4 micrometers absorption feature in this object (Lequeux & Jourdain de Muizon). The high resolution and high signal-to-noise ratio of our spectrum allow us to derive the detailed profile of this absorption feature, which is very similar to that observed in the spectrum of the Galactic center and also resembles the strong 3.4 micrometers emission feature in some post-asymptotic giant branch stars. A weak 3.3 micrometers unidentified infrared band, marginally detected in the CRL 618 spectrum of Lequeux & Jourdain de Muizon, is present in our spectrum. The existence of the 3.4 micrometers feature implies the presence of relatively short-chained, aliphatic hydrocarbon materials (-CH2-/-CH3 approximately = 2-2.5) in the circumstellar environment around CRL 618. It also implies that the carriers of the interstellar 3.4 micrometers feature are produced at least in part in circumstellar material, and it calls into question whether any are produced by the processing of interstellar ices in dense interstellar clouds, as has been previously proposed. Other features in the spectrum are recombination lines of hydrogen, rotational and vibration-rotation lines of molecular hydrogen, and a broad absorption probably due to a blend of HCN and C2H2 bands.

Spectroscopy, Near-Infrared↗
NASA NTRS1990

Infrared spectroscopy and Mie scattering of acetylene aerosols formed in a low temperature diffusion cell

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.

Dunder, T.↗
NASA NTRS1993

Surface chemistry of liquid metals

The fundamental surface chemistry of the behavior of liquid metals spreading on a solid substrate is not at all well understood. Each of these questions involves knowing the details of the structure of interfaces and their dynamics. For example the structure of a monolayer of tin oxide on pure liquid tin is unknown. This is in contrast to the relatively large amount of data available on the structure of copper oxide monolayers on solid, pure copper. However, since liquid tin has a vapor pressure below 10(exp -10)torr for a reasonable temperature range above its melting point, it is possible to use the techniques of surface science to study the geometric, electronic and vibrational structures of these monolayers. In addition, certain techniques developed by surface chemists for the study of liquid systems can be applied to the ultra-high vacuum environment. In particular we have shown that light scattering spectroscopy can be used to study the surface tension tensor of these interfaces. The tin oxide layer in particular is very interesting in that the monolayer is rigid but admits of bending. Ellipsometric microscopy allows the visualization of monolayer thick films and show whether island formation occurs at various levels of dosing.

Mann, J. Adin, Jr.↗
NASA NTRS2018

Detection Opportunity for Aromatic Signature in Titan's Aerosols in the 4.1-5.3 μm Range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100's of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In this Letter we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan's aerosol analogs. We introduce initial gas mixtures of (i) N2–C5H5N (100%/250 ppm), (ii) N2–CH4–C5H5N (99%/1%/250 ppm), and (iii) N2–CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1–5.3 μm (1850–2450 cm−1) spectral region, attributed to overtones of aromatic C–H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/Visual and Infrared Mapping Spectrometer (VIMS) instrument in the 1–5 μm infrared window.

Mathé, Christophe↗
NASA NTRS1987

Sub-Doppler tunable far-infrared spectroscopy

The first experimental observations of sub-Doppler linewidths in a cell made using tunable far-infrared radiation are reported. A double-resonance scheme has been used, combining CO2-laser infrared radiation with tunable far-infrared radiation to observe a sub-Doppler line shape in an excited vibrational state of CH3OH.

Inguscio, M.↗
NASA NTRS2001

Development of an Early Warning Fire Detection System using Correlation Spectroscopy

Combustion byproducts are numerous. A few examples of the gaseous byproducts include carbon dioxide, carbon monoxide, hydrogen chloride, hydrogen cyanide and ammonia. For detecting these chemical species, classic absorption spectroscopy has been used for many decades, but the sensitivity of steady-state methods is often unsuitable for the detection of trace compounds at the low levels (parts per million to parts per billion) appropriate for scientific purposes. This is particularly so for monitoring equipment, which must be compact and cost-effective, and which is often subjected to shock, vibration, and other environmental effects that can severely degrade the performance of high-sensitivity spectrometers in an aircraft. Steady-state techniques also suffer from a lack of specificity; the deconvolution of the spectra of complex mixtures is a laborious and error prone process. These problems are exacerbated in remote fiber-optic monitoring where, for practical reasons, the fundamental absorbance region of the spectrum (often between 3 and 8 microns) is inaccessible, and the low-strength, closely spaced, near-infrared overtone absorbance bands must be used. We circumvented these challenges by employing correlation spectroscopy, a variation of modulation spectroscopy.

Goswami, K.↗
NASA NTRS1974

High resolution interferometry of cool stars

A description is given of results obtained in a program of infrared high resolution spectroscopy of cool stars. The nature of infrared stellar spectra is considered along with questions regarding astrophysics and stellar infrared spectroscopy. An abundance analysis for alpha Ori (Betelgeuse) is conducted. The C-12/C-13 abundance ratio is examined and attention is given to the O-16/O-18 and O-16/O-17 abundance ratios. M stars and SiO vibration-rotation bands are discussed and questions regarding the characteristics of the molecular hydrogen quadrupole vibration-rotation lines are explored.

Lambert, D. L.↗
NASA NTRS1986

Raman Doppler velocimetry - A unified approach for measuring molecular flow velocity, temperature, and pressure

Molecular flow velocity (one component), translational temperature, and static pressure of N2 are measured in a supersonic wind tunnel using inverse Raman spectroscopy. For velocity, the technique employs the large Doppler shift exhibited by the molecules when the pump and probe laser beams are counterpropagating (backward scattering). A retrometer system is employed to yield an optical configuration insensitive to mechanical vibration, which has the additional advantage of simultaneously obtaining both the forward and backward scattered spectra. The forward and backward line breadths and their relative Doppler shift can be used to determine the static pressure, translational temperature, and molecular flow velocity. A demonstration of the technique was performed in a continuous airflow supersonic wind tunnel in which data were obtained under the following conditions: (1) free-stream operation at five set Mach number levels over the 2.50-4.63 range; (2) free-stream operation over a range of Reynolds number (at a fixed Mach number) to vary systematically the static pressure; and (3) operation in the flow field of a simple aerodynamic model to assess beam steering effects in traversing the attached shock layer.

Exton, R. J.↗
NASA NTRS1991

Nonequilibrium in a low power arcjet nozzle

Emission spectroscopy measurements were made of the plasma flow inside the nozzle of a 1-kW-class arcjet thruster. The thruster propellant was a hydrogen-nitrogen mixture used to simulate fully decomposed hydrazine. Atomic electron-excitation, vibrational, and rotational temperatures were determined for the expanding plasma using relative line intensity techniques. The atomic excitation temperature decreased from 18,000 K at a location 3 mm downstream of the constrictor to 9000 K at a location 9 mm from the constrictor, while the molecular vibrational and rotational temperatures decreased from 6500 K to 2500 K and from 8000 K to 3000 K, respectively, between the same locations. The electron density, measured using hydrogen H-beta line Stark broadening, decreased from about 10 to the 15th cu cm to about 2 x 10 to the 14th cu cm during the expansion. The results show that the plasma is highly nonequilibrium throughout the nozzle, with most relaxation times equal or exceeding the particle residence time.

Myers, Roger M.↗
NASA NTRS1992

Middle and upper atmosphere pressure-temperature profiles and the abundances of CO2 and CO in the upper atmosphere from ATMOS/Spacelab 3 observations

An improved method for retrieving pressure-temperature profiles is described and is used to retrieve profiles of the kinetic-temperature and atmospheric-pressure profiles between 20 and 116 km altitudes and the CO2 and CO volume-mixing ratios between 70 and 116 km, using the IR occultation spectra recorded by the Spacelab 3 atmospheric trace molecular spectroscopy (ATMOS) Fourier transform spectrometer between April 29 and May 6, 1985. Profiles are derived for six ATMOS occultations. The CO2 and CO volume-mixing profiles are compared with previous observations and model predictions. Evidence is found for vibrational non-LTE by analyzing the lines of the (nu-2 + nu-3 - nu-2) (C-12)(O-16) band. Results are used for deriving (C-12)(O-16) (010) vibrational temperatures, which are compared with the retrieved kinetic temperatures and the predictions of non-LTE effects by recent models.

Rinsland, C. P.↗
NASA NTRS2004

Multiplex coherent raman spectroscopy detector and method

A multiplex coherent Raman spectrometer (10) and spectroscopy method rapidly detects and identifies individual components of a chemical mixture separated by a separation technique, such as gas chromatography. The spectrometer (10) and method accurately identify a variety of compounds because they produce the entire gas phase vibrational Raman spectrum of the unknown gas. This is accomplished by tilting a Raman cell (20) to produce a high-intensity, backward-stimulated, coherent Raman beam of 683 nm, which drives a degenerate optical parametric oscillator (28) to produce a broadband beam of 1100-1700 nm covering a range of more than 3000 wavenumber. This broadband beam is combined with a narrowband beam of 532 nm having a bandwidth of 0.003 wavenumbers and focused into a heated windowless cell (38) that receives gases separated by a gas chromatograph (40). The Raman radiation scattered from these gases is filtered and sent to a monochromator (50) with multichannel detection.

Chen, Peter↗
NASA NTRS2009

Enhancing SERS by Means of Supramolecular Charge Transfer

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

Wong, Eric↗
NASA NTRS1990

Accurate frequency of the 119 micron methanol laser from tunable far-infrared absorption spectroscopy

High-accuracy absorption spectroscopy of CH3OH in the far infrared is discussed. In addition to 22 transitions in the ground state, the frequency of the (n, tau, J, K), (0, 1, 16, 8) to (0, 2, 15, 7) transition in the nu5 excited vibrational level, which is responsible for the laser emission at 119 microns, was measured. The measured frequency is 2,522,782.57(10) MHz at zero pressure, with a pressure shift of 6.1(32) kHz/Pa (0.805/420/ MHz/torr). An accurate remeasurement of the laser emission frequency has also been performed, and the results are in good agreement.

Inguscio, M.↗
NASA NTRS2011

A Laboratory and Theoretical Study of Silicon Hydroxide SiOH

The rotational spectrum of the triatomic free radical SiOH in its X 2A' ground electronic state has been observed in a supersonic molecular beam by Fourier transform microwave spectroscopy. The fundamental (10,1 yields 00,0) transition has been detected for normal SiOH and for three rare isotopic species: (30)SiOH, Si(18)OH, and SiOD. The same transition has also been observed in two of three excited vibrational states, v2 and v3, for the most abundant species. Precise spectroscopic constants, including those that describe the effective spin doubling and hydrogen hyperfine structure, have been derived for each isotopic species or vibrational state. To complement the laboratory work, theoretical calculations of the structure, dipole moment, and energies of the X 2A' and low-lying 1 2A'' states have also been undertaken at the coupled cluster level of theory. In agreement with theoretical predictions, we conclude from the hyperfine constants that SiOH is a best described as a pi-type radical, with the unpaired electron localized on a p orbital on the silicon atom. Assuming a bond angle of 118.5 deg, the Si-O bond length is 1.647(2) Angstroms and the O-H bond length is 0.969(4) Angstrom.

McCarthy, M. C.↗