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At least 19 records

On the possibility of measuring atmospheric OH using intracavity laser spectroscopy

Intracavity laser spectroscopy (ILS) has been demonstrated to be useful for measuring extremely weak absorption produced by gases in air. ILS is based on the observation that when there are spectrally narrow losses within the cavity of a broadband laser, the laser output has corresponding spectral holes where the laser oscillation is partially quenched. The depth of the laser output dips can be enhanced by a factor of 10(exp 5) over the depth of the initial cavity loss, and absorptivities of 10(exp -8) cm(exp -1) have been measured in lasers only one meter long. With ILS, one can achieve in a compact space a spectral contrast that would otherwise require kilometers of pathlength. ILS systems typically use quasi-continuous wave dye lasers operating close to threshold. The pump laser is modulated from just below to just above the threshold level for the dye laser, and the dye laser output is spectroscopically observed during a well defined time interval after the onset of lasing (the generation time). The spectral contrast of an intracavity absorber is equivalent to that produced by absorption through a path length equal to the generation time multiplied by the speed of light (assuming the cavity is completely filed with the absorber) up to some limiting time. Thus, if one measures the spectrum after 33 microseconds, the effective path length is 10,000 meters.

Mcmanus, J. Barry↗

Infrared vibration-rotation spectra of the ClO radical using tunable diode laser spectroscopy

Tunable diode laser spectroscopy is used to measure the infrared vibration-rotation spectra of the ClO radical. The radical is generated in a flow system where a Cl2-He mixture passes through a microwave discharge to dissociate the Cl2. An O3-O2 mixture from an ozone generator is injected into the system downstream of the microwave discharge where O3 combines with Cl to form ClO. By adjusting the gas flow rates to yield an excess of Cl atoms, all the ozone is combined. ClO concentration is measured with UV absorption at 2577 and 2772 A and a deuterium lamp as a continuous source. Total cell pressure is 5.5 torr. The diode laser spectrometer is calibrated with ammonia lines as a reference where possible. The frequency of vibration-rotation lines is expressed as a function of rotational quantum number, fundamental vibrational frequency, and the rotational constants of the upper and lower vibrational states.

Rogowski, R. S.↗

Development and Optical Testing of the Camera, Hand Lens, and Microscope Probe with Scannable Laser Spectroscopy (CHAMP-SLS)

Conducting high resolution field microscopy with coupled laser spectroscopy that can be used to selectively analyze the surface chemistry of individual pixels in a scene is an enabling capability for next generation robotic and manned spaceflight missions, civil, and military applications. In the laboratory, we use a range of imaging and surface preparation tools that provide us with in-focus images, context imaging for identifying features that we want to investigate at high magnification, and surface-optical coupling that allows us to apply optical spectroscopic analysis techniques for analyzing surface chemistry particularly at high magnifications. The camera, hand lens, and microscope probe with scannable laser spectroscopy (CHAMP-SLS) is an imaging/spectroscopy instrument capable of imaging continuously from infinity down to high resolution microscopy (resolution of approx. 1 micron/pixel in a final camera format), the closer CHAMP-SLS is placed to a feature, the higher the resultant magnification. At hand lens to microscopic magnifications, the imaged scene can be selectively interrogated with point spectroscopic techniques such as Raman spectroscopy, microscopic Laser Induced Breakdown Spectroscopy (micro-LIBS), laser ablation mass-spectrometry, Fluorescence spectroscopy, and/or Reflectance spectroscopy. This paper summarizes the optical design, development, and testing of the CHAMP-SLS optics.

Fluorescence↗

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

Worsnop, Douglas R.↗

Optical fringe reduction technique for FM laser spectroscopy

A simple fringe reduction method for FM diode laser spectroscopy is discussed. The fringes can be effectively suppressed by using a modulation frequency that is an integral multiple of the free spectral range of the fringes. The technique is experimentally confirmed by two-tone FM spectroscopy of water vapor absorption lines. A factor of 20 fringe reduction is observed.

Chou, Nee-Yin↗

Microgravity Diode Laser Spectroscopy Measurements in a Reacting Vortex Ring

The technique of Diode Laser Spectroscopy (DLS) with wavelength modulation is utilized to measure the concentration of methane in reacting vortex rings under microgravity conditions. From the measured concentration of methane, other major species such as water, carbon dioxide, nitrogen, and oxygen can be easily computed under the assumption of equilibrium chemistry with the method of Interactive Temperature with Assumed Chemistry (ITAC). The conserved scalar approach in modelling the coupling between fluid dynamics and combustion is utilized to represent the unknown variables in terms of the mixture fraction and scalar dissipation rate in conjunction with ITAC. Post-processing of the DLS measurements and the method of ITAC used in computing the species concentration are discussed. From the flame luminosity results, the increase in ring circulation appears to increase the fuel consumption rate inside the reacting vortex ring and the flame height for cases with similar fuel volumes. Preliminary results and application of ITAC show some potential capabilities of ITAC in DLS. The measured concentration of methane, and computed concentrations of water and carbon dioxide agree well with available results from numerical simulations.

Chen, Shin-Juh↗

Microgravity Diode Laser Spectroscopy Measurements in a Reacting Vortex Ring

The technique of Diode Laser Spectroscopy (DLS) with wavelength modulation is utilized to measure the concentration of methane in reacting vortex rings under microgravity conditions. From the measured concentration of methane, other major species such as water, carbon dioxide, nitrogen, and oxygen can be easily computed under the assumption of equilibrium chemistry with an iterative method called ITAC (Iterative Temperature with Assumed Chemistry). The conserved scalar approach in modelling the coupling between fluid dynamics and combustion is utilized to represent the unknown variables in terms of the mixture fraction and scalar dissipation rate in conjunction with ITAC. Post-processing of the DLS and the method used to compute the species concentration are discussed. From the flame luminosity results, ring circulation appears to increase the fuel consumption rate inside the reacting vortex ring and the flame height for cases with similar fuel volumes but different ring circulations. The concentrations of methane, water, and carbon dioxide agree well with available results from numerical simulations.

Chen, Shin-Juh↗

Laser Spectroscopy Multi-Gas Monitor: Results of Technology Demonstration on ISS

Tunable diode laser spectroscopy (TDLS) is an up and coming trace and major gas monitoring technology with unmatched selectivity, range and stability. The technology demonstration of the 4 gas Multi-Gas Monitor (MGM), reported at the 2014 ICES conference, operated continuously on the International Space Station (ISS) for nearly a year. The MGM is designed to measure oxygen, carbon dioxide, ammonia and water vapor in ambient cabin air in a low power, relatively compact device. While on board, the MGM experienced a number of challenges, unplanned and planned, including a test of the ammonia channel using a commercial medical ammonia inhalant. Data from the unit was downlinked once per week and compared with other analytical resources on board, notably the Major Constituent Analyzer (MCA), a magnetic sector mass spectrometer. MGM spent the majority of the time installed in the Nanoracks Frame 2 payload facility in front breathing mode (sampling the ambient environment of the Japanese Experiment Module), but was also used to analyze recirculated rack air. The capability of the MGM to be operated in portable mode (via internal rechargeable lithium ion polymer batteries or by plugging into any Express Rack 28VDC connector) was a part of the usability demonstration. Results to date show unprecedented stability and accuracy of the MGM vs. the MCA for oxygen and carbon dioxide. The ammonia challenge (approx. 75 ppm) was successful as well, showing very rapid response time in both directions. Work on an expansion of capability in a next generation MGM has just begun. Combustion products and hydrazine are being added to the measurable target analytes. An 8 to 10 gas monitor (aka Gas Tricorder 1.0) is envisioned for use on ISS, Orion and Exploration missions.

Mudgett, Paul D.↗

Design and Calibration of a Raman Spectrometer for use in a Laser Spectroscopy Instrument Intended to Analyze Martian Surface and Atmospheric Characteristics for NASA

This project's goal is the design of a Raman spectroscopy instrument to be utilized by NASA in an integrated spectroscopy strategy that will include Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Induced Florescence Spectroscopy (LIFS) for molecule and element identification on Mars Europa, and various asteroids. The instrument is to be down scaled from a dedicated rover mounted instrument into a compact unit with the same capabilities and accuracy as the larger instrument. The focus for this design is a spectrometer that utilizes Raman spectroscopy. The spectrometer has a calculated range of 218 nm wavelength spectrum with a resolution of 1.23 nm. To filter out the laser source wavelength of 532 nm the spectrometer design utilizes a 532 nm wavelength dichroic mirror and a 532 nm wavelength notch filter. The remaining scatter signal is concentrated by a 20 x microscopic objective through a 25-micron vertical slit into a 5mm diameter, 1cm focal length double concave focusing lens. The light is then diffracted by a 1600 Lines per Millimeter (L/mm) dual holographic transmission grating. This spectrum signal is captured by a 1-inch diameter double convex 3 cm focal length capture lens. An Intensified Charge Couple Device (ICCD) is placed within the initial focal cone of the capture lens and the Raman signal captured is to be analyzed through spectroscopy imaging software. This combination allows for accurate Raman spectroscopy to be achieved. The components for the spectrometer have been bench tested in a series of prototype developments based on theoretical calculations, alignment, and scaling strategies. The mounting platform is 2.5 cm wide by 8.8 cm long by 7 cm height. This platform has been tested and calibrated with various sources such as a neon light source and ruby crystal. This platform is intended to be enclosed in a ruggedized enclosure for mounting on a rover platform. The size and functionality of the Raman spectrometer allows for the rover to carry other mission critical devices. This project will be continued at NASA until the requirements are met for the expected initial 2020 launch date.

Lucas, John F.↗

Laboratory diode laser spectroscopy in molecular planetary astronomy

Infrared spectroscopy of planetary atmospheres is performed at high spectral resolution comparable to that in the laboratory. This requires that laboratory spectroscopy use the highest resolution and the most accurate techniques. Tunable diode laser spectroscopy can supply many of the spectroscopic parameters needed by astronomers. In particular, line positions, line strengths, and collisional line widths are measured with diode lasers, and these are often among the best values available. Diode laser spectra are complimentary to lower resolution, broader-coverage Fourier transform spectra. Certain procedures must be adopted, however, when using diode lasers, for determining their output characteristics and for calibrating each spectrum against quality references.

Jennings, D. E.↗

Stratospheric composition measurements of earth and Titan using high-resolution tunable diode laser spectroscopy

Field and laboratory measurements of species of atmospheric interest made as part of the JPL diode laser spectroscopy program are presented. Stratospheric measurements of NO2, NO, CO2, and H2O made in November 1985 using the BLISS instrument are reported, together with recent laboratory measurements of spectral line parameters of HNO3 and HO2NO2. In addition, a novel diode laser instrument concept for the in situ sensing of Titan's atmosphere is described for the Saturn Orbiter/Titan Probe (SOTP) Cassini Mission.

Webster, Christopher R.↗

Oxygen Spectroscopy Laser Sounding Instrument for Remote Sensing of Atmospheric Pressure

We report on the progress of an Oxygen spectroscopy laser sounding instrument designed as a calibration channel for a carbon dioxide (CO2) laser sounding instrument. We have developed a pulsed, frequency-doubled, fiber laser transmitter for use in an oxygen instrument. The instrument concept uses the pressure broadening of spectroscopic lines of the diatomic oxygen A-band to deduce atmospheric pressure. There are many uses for this measurement but we are developing it primarily to make a measurement of the dry mixing ratio of CO2. The CO2 measurement can be affected by changes in atmospheric properties such as humidity, temperature and pressure. To remove these variances requires measuring a stable, well-mixed gas like Oxygen. We will report on the basic theory behind the instrument, measurements made at a test site at Goddard, review the current state of the instrument technologies and the necessary steps to bring them to space readiness, and review the current state of the instrument development.

Stephen Mark A.↗

Characterization of silicon-carbon clusters by infrared laser spectroscopy. The nu 1 band of SiC4

The nu 1 fundamental vibration of linear SiC4 has been observed by infrared diode laser spectroscopy of a supersonic cluster beam. Twenty-four rovibrational transitions were measured in the spectral region of 2094.6 to 2097.1 cm-1, the rotational temperature was 10 K. A combined least-squares fit of these transitions with previously reported microwave data yielded the following molecular constants: nu 1 = 2095.45806(37) cm-1, B" = 0.051161131(52) cm-1, and B' = 0.0509157(96) cm-1. These results are compared to vibrational spectroscopy measurements of SiC4 trapped in a solid Ar matrix and to ab initio calculations.

NASA Discipline Exobiology↗

An experiment concept to measure stratospheric trace constituents by laser heterodyne spectroscopy

Laser heterodyne spectroscopy (LHS) techniques were used to measure radical gases from Spacelab. Major emphasis was placed on the measurement of ClO, ClOnO2, HO2, H2O2, N2O5, and HOCl in solar occultation with vertical resolution less than or equal to 2-km and vertical range from 1O to 70-km. Sensitivity analyses were performed on ClO and O3 to determine design criteria for the LHS instrument. Results indicate that O3 and ClO vertical profiles can be measured with an accuracy more than or equal to 95% and more than or equal to 80%, respectively, over the total profile.

Allario, F.↗

Stable isotope laser spectroscopy

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.

Becker, J. F.↗

Infrared laser spectroscopy of jet-cooled carbon clusters - The bending dynamics of linear C9

We report improved measurements for the nu6 antisymmetric stretch fundamental and observation of the (nu6 + nu15) - nu15 and (nu6 + 2nu15) - 2nu15 hot bands of the linear C9 carbon cluster by direct absorption diode laser spectroscopy of a supersonic carbon cluster beam. Analysis of these bands characterizes C9 as a semirigid molecule with a bending potential similar to that of C5 and further evidences the alternation in degree of rigidity of linear carbon clusters with the g-u symmetry of the HOMO.

Van Orden, A.↗

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↗

Methane overtone absorption by intracavity laser spectroscopy

Interpretation of planetary methane (CH4) visible-near IR spectra, used to develop models of planetary atmospheres, has been hampered by a lack of suitable laboratory spectroscopic data. The particular CH4 spectral bands are due to intrinsically weak, high overtone-combination transitions too complex for classical spectroscopic analysis. The traditional multipass cell approach to measuring spectra of weakly absorbing species is insufficiently sensitive to yield reliable results for some of the weakest CH4 absorption features and is difficult to apply at the temperatures of the planetary environments. A time modulated form of intracavity laser spectroscopy (ILS), has been shown to provide effective absorption pathlengths of 100 to 200 km with sample cells less than 1 m long. The optical physics governing this technique and the experimental parameters important for obtaining reliable, quantitative results are now well understood. Quantitative data for CH4 absorption obtained by ILS have been reported recently. Illustrative ILS data for CH4 absorption in the 619.7 nm and 681.9 nm bands are presented. New ILS facilities at UM-St. Louis will be used to measure CH4 absorption in the 700 to 1000 nm region under conditions appropriate to the planetary atmospheres.

Obrien, James J.↗