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All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Infrared Spectroscopy as a Chemical Fingerprinting Tool

Infrared (IR) spectroscopy is a powerful analytical tool in the chemical fingerprinting of materials. The technique is rapid, reproducible and usually non-invasive. With the appropriate accessories, the technique can be used to examine samples in either a solid, liquid or gas phase. Solid samples of varying sizes and shapes may be used, and with the addition of microscopic IR (microspectroscopy) capabilities, minute materials such as single fibers and threads may be examined. With the addition of appropriate software, microspectroscopy can be used for automated discrete point or compositional surface area mapping, with the latter providing a means to record changes in the chemical composition of a material surface over a defined area. Both aqueous and non-aqueous free-flowing solutions can be analyzed using appropriate IR techniques, as can viscous liquids such as heavy oils and greases. Due to the ability to characterize gaseous samples, IR spectroscopy can also be coupled with thermal processes such as thermogravimetric (TG) analyses to provide both thermal and chemical data in a single run. In this configuration, solids (or liquids) heated in a TG analyzer undergo decomposition, with the evolving gases directed into the IR spectrometer. Thus, information is provided on the thermal properties of a material and the order in which its chemical constituents are broken down during incremental heating. Specific examples of these varied applications will be cited, with data interpretation and method limitations further discussed.

Huff, Tim↗
NASA NTRS1984

Infrared spectroscopy of interstellar shocks

Infrared emission lines from interstellar shocks provide valuable diagnostics for violent events in the interstellar medium, such as supernova remnants and mass outflow from young stellar objects. There are two types of interstellar shocks: in J shocks, gas properties 'jump' from their preshock to their postshock values in a shock front with a thickness equal to or less than one mean free path; radiation is emitted behind the shock front, primarily in the visible and ultraviolet, but with a few strong infrared lines, such as OI(63 microns). Such shocks occur in ionized or neutral atomic gas, or at high velocities (equal to or greater than 50 km/s) in molecular gas. In C shocks, gas is accelerated and heated by collisions between charged particles, which have a low concentration and are coupled to the magnetic field, and neutral particles; radiation is generated throughout the shock and is emitted almost entirely in infrared emission lines. Such shocks occur in weakly ionized molecular gas for shock velocities below about 50 km/s.

Mckee, C. F.↗
NASA NTRS1989

Far-infrared spectroscopy of galaxies

Far infrared (FIR) spectral line emission from galaxies is discussed with respect to past, present and near future observations. A review of the importance of the FIR lines as probes of the interstellar medium is presented. The various fine structure emission lines detected from the archetypal starburst galaxy M82, and the (C II) line radiation which is now observed toward a large variety of external galaxies are discussed. The improvements allowed by the advent of the Stratospheric Observatory For Infrared Astronomy (SOFIA), the Infrared Space Observatory (ISO) and the Space Infrared Telescope Facility (SIRTF) are underlined.

Stacey, G. J.↗
NASA NTRS2004

Jupiter's atmospheric composition from the Cassini thermal infrared spectroscopy experiment

The Composite Infrared Spectrometer observed Jupiter in the thermal infrared during the swing-by of the Cassini spacecraft. Results include the detection of two new stratospheric species, the methyl radical and diacetylene, gaseous species present in the north and south auroral infrared hot spots; determination of the variations with latitude of acetylene and ethane, the latter a tracer of atmospheric motion; observations of unexpected spatial distributions of carbon dioxide and hydrogen cyanide, both considered to be products of comet Shoemaker-Levy 9 impacts; characterization of the morphology of the auroral infrared hot spot acetylene emission; and a new evaluation of the energetics of the northern auroral infrared hot spot.

Hydrocarbons↗
NASA NTRS2005

First Light from the Far-Infrared Spectroscopy of the Troposphere (FIRST) Instrument

We present first light spectra from the new Far-Infrared Spectroscopy of the Troposphere (FIRST) instrument. FIRST is a Fourier Transform Spectrometer developed to measure accurately the far-infrared (15 to 100 micrometers; 650 to 100 wavenumbers) emission spectrum of the Earth and its atmosphere. The observations presented here were obtained during a high altitude balloon flight from Ft. Sumner, New Mexico on 7 June 2005. The flight data demonstrate the instrument's ability to observe the entire energetically significant infrared emission spectrum (50 to 2000 wavenumbers) at high spectral and spatial resolution on a single focal plane in an instrument with one broad spectral bandpass beamsplitter. Comparisons with radiative transfer calculations demonstrate that FIRST accurately observes the very fine spectral structure in the far-infrared. Comparisons of the atmospheric window radiances measured by FIRST and by instruments on the NASA Aqua satellite that overflew FIRST are in excellent agreement. FIRST opens a new window on the spectrum that can be used for studying atmospheric radiation and climate, cirrus clouds, and water vapor in the upper troposphere.

Mlynczak, Martin G.↗
NASA NTRS1972

Atmospheric and surface properties of Mars obtained by infrared spectroscopy on Mariner 9

During the eleven month operational lifetime of Mariner 9, the infrared spectroscopy experiment obtained data over a large portion of Mars. Recently obtained spectra indicate that strong seasonal variations in the water vapor distribution over both polar regions occurred. The wettest atmospheric conditions observed so far contain 20 to 30 precipitable microns of water over the north polar cap during northern spring. A low resolution pressure map is presented which covers that portion of the planet between latitudes -60 deg and +25 deg. A more detailed study of the Coprates canyon indicates that at its lowest point the canyon floor must be at least 5 km below the rim. Applications of tidal theory to temperature fields derived from the spectra indicate diurnal surface pressure fluctuations of as much as 12 percent during the great dust storm of 1971-72. Qualitative arguments based on radiative transfer calculations for model dust clouds composed of spherical quartz particles suggest that particle radii during the storm were of the order of a few microns.

Conrath, B.↗
NASA NTRS1973

Atmospheric and surface properties of Mars obtained by infrared spectroscopy on Mariner 9.

During the almost 1-year operational lifetime of Mariner 9 the infrared spectroscopy experiment obtained data over a large portion of Mars. Between June and October 1972, improvements were made in the CO2 transmittances, which are necessary for the interpretation of the thermal emission spectra. Recently obtained spectra indicate that strong seasonal variations in the water vapor distribution occurred over both polar regions. The wettest atmospheric conditions observed so far contain 20 to 30 precipitable microns of water over the north polar cap during northern spring. A low-resolution pressure map is presented that covers that portion of the planet between latitudes -60 and +25 deg. A more detailed study of the Coprates canyon indicates that, at its lowest point, the canyon floor must be at least 5 km below the rim. Applications of tidal theory to temperature fields derived from the spectra indicate diurnal surface pressure fluctuations of as much as 12% during the Great Dust Storm of 1971-1972.

Conrath, B.↗
NASA NTRS1994

Near-infrared spectroscopy of proto-planetary nebulae

Sixteen proto-planetary nebulae were observed with low-resolution infrared spectroscopy in the H and K bands, and four were observed in the L band. In the H band, most of the objects show hydrogen Brackett lines (from n = 10 goes to 4 to n = 20 goes to 4) in absorption. In the K band, absorption bands (delta (nu) = 2) of CO were observed to as high as nu = 6 goes to 4, and in three cases the CO bands are in emission. The CO spectrum of 22272 + 5435 was found to change from emission to absorption over a 3 month interval. The CO emission most likely arises from collisional excitation resulting from recent episodes of mass loss. One new object which possibly shows weak 3.3 micron emission was found.

Hrivnak, Bruce J.↗
DOE OSTI2024

Development of a Platform for High-Resolution Ion Mobility Separations Coupled with Messenger Tagging Infrared Spectroscopy for High-Precision Structural Characterizations

The ability to uniquely identify a compound requires highly precise and orthogonal measurements. Here we describe a newly developed analytical platform that integrates high resolution ion mobility and cryogenic vibrational ion spectroscopy for high-precision structural characterizations. This platform allows for the temporal separation of isomeric/isobaric ions and provides a highly sensitive description of the ion’s adopted geometry in the gas phase. The combination of these orthogonal structural measurements yields precise descriptors that can be used to resolve between and confidently identify highly similar ions. The unique benefits of our instrument, which integrates a structures for lossless ion manipulations ion mobility (SLIM IM) device with messenger tagging infrared spectroscopy, include the ability to perform high-resolution ion mobility separations and to record the IR spectra of all ions simultaneously. The SLIM IM device, with its 13 m separation path length, allows for multipass experiments to be performed for increased resolution as needed. It is integrated with an Agilent qTOF MS where the collision cell was replaced with a cryogenically held (30 K) TW-SLIM module. The cryo-SLIM is operated in a novel manner that allows ions to be streamed through the device and collisionally cooled to a temperature where they can form noncovalently bound N 2 complexes that are maintained as they exit the device and are detected by the TOF mass analyzer. The instrument can be operated in two modes: IMS+IR where the IR spectra for mobility-selected ions can be recorded and IR-only mode where the IR spectra for all mass-resolved ions can be recorded. In IR-only mode, IR spectra (400 cm –1 spectral range) can be recorded in as short as 2 s for high throughput measurements. Further, this work details the construction of the instrument and modes of operation. It provides initial benchmarking of CCS and IR measurements to demonstrate the utility of this instrument for targeted and untargeted approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR studies (telescopic and laboratory) have demonstrated that much of the carbon in the interstellar medium (ISM) is in complex organic species of a variety of types, but the distribution, abundance, and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEAST mission concept designed to conduct IR spectroscopic observations to detect and identify these materials to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. Systematic studies include the observation of planetary nebulae and stellar outflows, protostellar objects, Solar System Objects, and galaxies, and multiple lines of sight through dense molecular clouds and the diffuse ISM. ABE will also search for evidence of D enrichment in complex molecules in all these environments. The mission is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cryogenic cross-dispersed spectrographs that share a single common slit. The 3 spectrometers each measure single spectral octaves (2.5-5, 5-10, 10-20 microns) and together cover the entire 2.5 - 20 micron region simultaneously. The spectrometers use state-of-the-art 1024x1024 pixel detectors, with a single InSb array for the 2.5-5 micron region and two Si:As arrays for the 5-10 and 10-20 micron regions. The spectral resolution is wavelength dependent but is greater than 2000 across the entire spectral range. ABE would operate in a heliocentric, Earth drift-away orbit and is designed to take maximum advantage of this environment for cooling, thermal stability, and mission lifetime. ABE would have a core science mission lasting approximately 1.5 years.

Sandford, Scott A.↗
NASA NTRS2002

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR telescopic and laboratory studies have shown that much of the carbon in the interstellar medium (ISM) is in complex organic species but the distribution, abundance and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept designed to conduct IR spectroscopic observations to detect and identify these materials and address outstanding problems in astrobiology, astrochemistry, and astrophysics. ABE's core science program includes observations of planetary nebulae and stellar outflows, protostellar objects, Solar System objects, and galaxies, and lines of sight through dense molecular clouds and the diffuse ISM. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cross-dispersed R-2000 spectrometers that share a single common slit. Each spectrometer measures one spectral octave and together cover the entire 2.5-20 micron region simultaneously. The spectrometers use state-of-the-art InSb and Si:As 1024x1024 pixel detectors. ABE would operate in a heliocentric, Earth drift-away orbit and have a core science mission lasting approximately 1.5 years. ABE is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp.

Sandford, Scott A.↗
NASA NTRS2003

Differences in the hemodynamic response to event-related motor and visual paradigms as measured by near-infrared spectroscopy

Several current brain imaging techniques rest on the assumption of a tight coupling between neural activity and hemodynamic response. The nature of this neurovascular coupling, however, is not completely understood. There is some evidence for a decoupling of these processes at the onset of neural activity, which manifests itself as a momentary increase in the relative concentration of deoxyhemoglobin (HbR). The existence of this early component of the hemodynamic response function, however, is controversial, as it is inconsistently found. Near infrared spectroscopy (NIRS) allows quantification of levels of oxyhemoglobin (HbO(2)) and HbR during task performance in humans. We acquired NIRS data during performance of simple motor and visual tasks, using rapid-presentation event-related paradigms. Our results demonstrate that rapid, event-related NIRS can provide robust estimates of the hemodynamic response without artifacts due to low-frequency signal components, unlike data from blocked designs. In both the motor and visual data the onset of the increase in HbO(2) occurs before HbR decreases, and there is a poststimulus undershoot. Our results also show that total blood volume (HbT) drops before HbO(2) and undershoots baseline, raising a new issue for neurovascular models. We did not find early deoxygenation in the motor data using physiologically plausible values for the differential pathlength factor, but did find one in the visual data. We suggest that this difference, which is consistent with functional magnetic resonance imaging (fMRI) data, may be attributable to different capillary transit times in these cortices.

NASA Program Biomedical Research and Countermeasur↗
NASA NTRS1982

Infrared heterodyne spectroscopy

Infrared heterodyne spectroscopy is an extremely useful tool for Doppler-limited studies of atomic and molecular lines in diverse astrophysical regions. The current state of the art is reviewed, and the analysis of CO2 lines in the atmosphere of Mars is outlined. Doppler-limited observations have enabled the discovery of natural laser emission in the mesosphere of Mars and the discovery of failure of local thermodynamic equilibrium near the surface of Mars.

Mumma, M. J.↗
NASA NTRS2010

Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy

Infrared heterodyne spectra of isotopic CO2 in the Martian atmosphere were obtained using the Goddard Heterodyne Instrument for Planetary Wind and Composition, HIPWAC, which was interfaced with the 3-meter telescope at the NASA Infrared Telescope Facility- Spectra were colle cted at a resolution of lambda/delta lambda=10(exp 7). Absorption fea tures of the CO2 isotopologues have been identified from which isotop ic ratios of oxygen have been determined. The isotopic ratios O-17/O -16 and O-18/O-16 in the Martian atmosphere can be related to Martian atmospheric evolution and can be compared to isotopic ratios of oxyg en in the Earth's atmosphere. Isotopic carbon and oxygen are importa nt constraints on any theory for the erosion of the Martian primordia l atmosphere and the interaction between the atmosphere and surface o r subsurface chemical reservoirs. This investigation explored the pr esent abundance of the stable isotopes of oxygen in Mars' atmospheric carbon dioxide by measuring rovibrational line absorption in isotop ic species of CO2 using groundbased infrared heterodyne spectroscopy in the vicinity of the 9.6 micron and 10.6 micron CO2 lasing bands. T he target transitions during this observation were O-18 C-12 O-16 as well as O-178 C-12 O-16 and O-16 C-113 O-16 at higher resolving power of lambda/delta lambda=10(exp 7) and with high signal-to-noise ratio (longer integration time) in order to fully characterize the absorpt ion line profiles. The fully-resolved lineshape of both the strong n ormal-isotope and the weak isotopic CO2 lines were measured simultane ously in a single spectrum.

Smith, R. L.↗
NASA NTRS2015

The Compositional Evolution of C/2012 S1 (ISON) from Ground-Based High-Resolution Infrared Spectroscopy as Part of a Worldwide Observing Campaign

Volatile production rates, relative abundances, rotational temperatures, and spatial distributions in the coma were measured in C/2012 S1 (ISON) using long-slit high-dispersion (lambda/delta lambda approximately 2.5 times 10 (sup 4)) infrared spectroscopy as part of a worldwide observing campaign. Spectra were obtained on Universal Time 2013 October 26 and 28 with NIRSPEC (Near Infrared Spectrometer) at the W.M. Keck Observatory, and Universal Time 2013 November 19 and 20 with CSHELL (Cryogenic Echelle Spectrograph) at the NASA IRTF (Infrared Telescope Facility). H2O was detected on all dates, with production rates increasing markedly from (8.7 plus or minus 1.5) times 10 (sup 27) molecules per second on October 26 (Heliocentric Distance = 1.12 Astronomical Units) to (3.7 plus or minus 0.4) times 10 (sup 29) molecules per second on November 20 (Heliocentric Distance = 0.43 Astronomical Units). Short-term variability of H2O production is also seen as observations on November 19 show an increase in H2O production rate of nearly a factor of two over a period of about 6 hours. C2H6, CH3OH and CH4 abundances in ISON (International Scientific Optical Network) are slightly depleted relative to H2O when compared to mean values for comets measured at infrared wavelengths. On the November dates, C2H2, HCN and OCS abundances relative to H2O appear to be within the range of mean values, whereas H2CO and NH3 were significantly enhanced. There is evidence that the abundances with respect to H2O increased for some species but not others between October 28 (Heliocentric Distance = 1.07 Astronomical Units) and November 19 (Heliocentric Distance = 0.46 Astronomical Units). The high mixing ratios of H2CO to CH3OH and C2H2 to C2H6 on November 19, and changes in the mixing ratios of some species with respect to H2O between October 28 to November 19, indicates compositional changes that may be the result of a transition from sampling radiation-processed outer layers in this dynamically new comet to sampling more pristine natal material as the outer processed layer was increasingly eroded and the thermal wave propagated into the nucleus as the comet approached perihelion for the first time. On November 19 and 20, the spatial distribution for dust appears asymmetric and enhanced in the antisolar direction, whereas spatial distributions for volatiles (excepting CN) appear symmetric with their peaks slightly offset in the sunward direction compared to the dust. Spatial distributions for H2O, HCN, C2H6, C2H2, and H2CO on November 19 show no definitive evidence for significant contributions from extended sources; however, broader spatial distributions for NH3 and OCS may be consistent with extended sources for these species. Abundances of HCN and C2H2 on November 19 and 20 are insufficient to account for reported abundances of CN and C2 in ISON near this time. Differences in HCN and CN spatial distributions are also consistent with HCN as only a minor source of CN in ISON on November 19 as the spatial distribution of CN in the coma suggests a dominant distributed source that is correlated with dust and not volatile release. The spatial distributions for NH3 and NH2 are similar, suggesting that NH3 is the primary source of NH2 with no evidence of a significant dust source of NH2; however, the higher production rates derived for NH3 compared to NH2 on November 19 and 20 remain unexplained. This suggests a more complete analysis that treats NH2 as a distributed source and accounts for its emission mechanism is needed for future work.

Russo, N. Dello↗
NASA NTRS1977

The Voyager infrared spectroscopy and radiometry investigation

Two interferometers covering the spectral ranges 17 to 170 microns and 1.4 to 10 microns and a radiometer covering the range 0.4 to 1.2 microns are employed in the Voyager infrared spectroscopy and radiometry investigation. The study will focus on cloud and gas composition of planets and satellites with substantial atmospheres (including isotopic ratios), haze scale height, atmospheric vertical thermal structure, local and planetary circulation, and planetary energy balance. Surface temperatures and thermal properties of satellites with tenuous atmospheres will also be assessed, and the particle size distribution and thermal characteristics of Saturn's rings will be analyzed.

Hanel, R.↗