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NASA NTRS1983

Tunable diode laser optogalvanic spectroscopy of molecules

The laser optogalvanic (LOG) technique for studying molecular spectra has been extended for the first time to the infrared wavelength region. Portions of the NH3 nu-2 band at 9.5 microns and the NO2 nu-3 band at 6.2 microns have been recorded at Doppler-limited resolution using CW tunable diode lasers to probe dc electrical discharges in pure NH3 and an NO2/He gas mixture. Using adjustable electrode positions and an orthogonal geometry between the probe laser and the discharge axis, two contributions to the optogalvanic signal are identified: one which corresponds to an increase in discharge impedance and is seen only for irradiation of the negative glow region; and a second which corresponds to a decrease in discharge impedance and is seen for irradiation of all other discharge regions.

Webster, C. R.↗

NASA NTRS1972

Upper atmospheric probing by resonance fluorescence excited by tunable laser radiation.

Consideration of the application of the measurement of resonance fluorescence radiation excited by tunable laser radiation to the detection of atomic, molecular, and ionic species in the upper atmosphere. The species considered are N2, N2(+), NO, NO(+), O2(+), CO, CO(+), CH, Na, K, and Ca. Calculations of the resonance scattering cross sections, photon returns, and signal-to-noise ratios are given for these species for a range of conditions. Based on a probing altitude of 100 km, the detections of N2, NO, CO, CH, O2, and the trace metals appear feasible with state-of-the-art systems and within the concentration range present in the atmosphere.

Saunders, A. R.↗

NASA NTRS1991

Calibration of a tunable excimer laser using the optogalvanic effect

A device for the calibration of a tunable excimer laser is currently under development. The laser provides UV radiation at three principal wavelengths, 193, 248, and 308 nm and is tunable over a range of 1 nm at each of these wavelengths. The laser is used as a non-intrusive optical probe to excite electronic transitions, and thereby induce fluorescence, of the principle molecules or atoms of interest in supersonic flowfields, both reacting and nonreacting. The fluorescence resulting from the excitation is observed with an intensified camera. Over the range of tunability at the three wavelengths are a number of transitions that can be observed. The intensity of the fluorescence depends in part on the local temperature and density. The nature of this thermodynamic dependence is variable among transitions; thus, identification of the transition under observation is required. The specific transition excited corresponds directly to the wavelength of the radiation. The present technique used for transition identification consists of scanning the laser across the range of tunability and observing the fluorescence resulting from various molecular transitions.

Abbitt, John D.↗

NASA NTRS2003

Novel High Efficient Organic Photovoltaic Materials

Solar energy is a renewable, nonpolluting, and most abundant energy source for human exploration of a remote site or outer space. In order to generate appreciable electrical power in space or on the earth, it is necessary to collect sunlight from large areas and with high efficiency due to the low density of sunlight. Future organic or polymer (plastic) solar cells appear very attractive due to their unique features such as light weight, flexible shape, tunability of energy band-gaps via versatile molecular or supramolecular design, synthesis, processing and device fabrication schemes, and much lower cost on large scale industrial production. It has been predicted that supramolecular and nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration due to improved electronic ultrastructure and morphology in comparison to polymer composite system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel block copolymer system containing donor and acceptor blocks covalently attached. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (RO-PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (SF-PPV). The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block has a strong PL emission at around 560 nm, and acceptor block has a strong PL emission at around 520 nm, the PL emissions of final block copolymers are severely quenched. This verifies the expected electron transfer and charge separation due to interfaces of donor and acceptor nano phase separated blocks. The system therefore has potential for variety light harvesting applications, including high efficient photovoltaic applications.

Sun, Sam↗

NASA NTRS1983

Supersonic-nitrogen flow-field measurements with the resonant Doppler velocimeter

The application of the resonant Doppler velocimeter (RDV) for obtaining the mean velocity, temperature, and pressure measurements and flow-field visualization in a supersonic free nitrogen jet is reported. This method utilizes laser-induced fluorescence to determine the spectral absorption of an atomic or molecular species seeded into the flow. A narrow linewidth tunable laser is directed into the flow and the total fluorescence from any point is obtained as the laser is tuned. The velocity of the flow is obtained from the Doppler shifted absorption frequency, and the temperature and pressure of the gas are determined from line broadening measurements. Results are presented for the use of this technique to determine the velocity, temperature, and pressure of the flow of sodium atoms seeded into a supersonic nitrogen jet. It is concluded that the visible signal is sufficiently intense for spatially resolved flow visualization purposes.

Cheng, S.↗

NASA NTRS1983

Vibration-rotation line strengths of the gas-phase OH radical

Absorption line strengths have been measured at 295 K for the first time for four vibration-rotation transitions of the OH radical, using a tunable, infrared diode-laser in conjunction with a molecular modulation spectrometer. A periodically varying OH concentration was created by photolysis, using a sinusoidally modulated 2537-A Hg lamp, of a flowing mixture of O3 and H2O contained within a quartz-walled White cell. The modulated absorption owing to the OH radical was subsequently observed by phase-sensitive detection. The absolute modulation amplitude of the OH number density was obtained by numerical simulation of the complete time-dependent photochemical system. The strongest transition measured was at 3407.607 kaysers, with a strength of 3.3 + or - 1.5 x 10 to the -20th per(cm molecule) sq cm.

Podolske, J.↗

NASA NTRS1991

Tunable far infrared laser spectrometers

The state of the art in far infrared (FIR) spectroscopy is reviewed. The development of tunable, coherent FIR radiation sources is discussed. Applications of tunable FIR laser spectrometers for measurement of rotational spectra and dipole moments of molecular ions and free radicals, vibration-rotation-tunneling spectra of weakly bound complexes, and vibration-rotation spectra of linear carbon clusters are presented. A detailed description of the Berkeley tunable FIR laser spectrometers is presented.

Blake, G. A.↗

NASA NTRS1973

Determination of Spatial Distribution of Air Pollution by Dye Laser Measurement of Differential Absorption of Elastic Backscatter

This paper presents the results of an analytical study of a lidar system which uses tunable organic dye lasers to accurately determine spatial distribution of molecular air pollutants. Also described will be experimental work to date on simultaneous multiwavelength output dye laser sources for this system. Basically the scheme determines the concentration of air pollutants by measuring the differential absorption of an (at least) two wavelength lidar signal elastically backscattered by the atmosphere. Only relative measurements of the backscattered intensity at each of the two wavelengths, one on and one off the resonance absorption of the pollutant in question, are required. The various parameters of the scheme are examined and the component elements required for a system of this type discussed, with emphasis on the dye laser source. Potential advantages of simultaneous multiwavelength outputs are described. The use of correlation spectroscopy in this context is examined. Comparisons are also made for the use of infrared probing wavelengths and sources instead of dye lasers. Estimates of the sensitivity and accuracy of a practical dye laser system of this type, made for specific pollutants, snow it to have inherent advantages over other schemes for determining pollutant spatial distribution.

Ahmed, S. A.↗

NASA NTRSDate not supplied

Phase Change Materials for Photonics in NASA Science and Space Missions

Phase change materials (PCMs) such as Ge2Sb2Te5, Ge2Sb2Se4Te1, and Sb2S3have recently emerged as a promising platform to control light on-chip due to their fast, dramatic, and reversible change in refractive index. Significant technical progress in the field has been achieved in terms of improving optical transparency, controlling PCMs both optically and electrically, and integrating with complex photonic circuits, leading to exciting applications. When PCMs are mated with metasurfaces, devices are capable of controlling the phase and amplitude of propagating light with arrays of subwavelength structures. These enhance tunability and reconfigurability and continue to redefine the boundaries of optical sciences. PCM-based metasurface optics also help to accelerate the adoption of new architectures with reduced size, weight, and power (SWaP) for science and space mission platforms at NASA. In this talk, I will introduce two NASA-lead PCM photonic projects: 1. P-ACTIVE (PCM-based actively tunable filter) for broad imaging and sensing applications – from probing molecular vibrations in chemical species to detecting radiant thermal signatures of the space launch system. 2. PROWESS (Phase change reconfigurable optical wavefront synthesis system) as a beam steerer for both Earth and space LiDAR and free space optical communication applications. From this seminar, the attendees will be exposed not only to PCM-based photonic technologies but also NASA missions including the MISSE (Materials on the International Space Station Experiment) test campaign that was conducted to expose PCMs and PCM-based metasurfaces in space for 6 months in 2022.

phase change material↗

NASA NTRS1994

A Spectral Atlas of the Nu(sub 12) Fundamental of (13)C(12)CH6 in the 12 Micron Region

The recent discovery of the minor isotopomer of ethane, (13)C(12)CH6, in the planetary atmospheres of Jupiter and Neptune, added ethane to the molecules which can be used to determine isotopic (12)C(12)C ratios for the jovian planets. The increased spectral resolution and coverage of the IR and far-IR instruments to be carried on the Cassini mission to Saturn and Titan may enable the detection of the minor isotopomer. Accurate frequency and cross-section measurements of the nu(sub 12) fundamental under controlled laboratory condition are important to interpret current and future planetary spectra. High resolution spectra of the minor isotopomer (13)C(12)CH6 have been recorded in the 12.2 micron region using the Kitt Peak Fourier Transform (FTS) and the Goddard Tunable Diode Laser spectrometer (TDL). In a global fit to 19 molecular constants in a symmetric top Hamiltonian, transition frequencies of the nu(sub 12) fundamental ranging up to J=35 and K=20 have been determined with a standard deviation of less than 0.0005 cm(exp -1). From selected line intensity measurements, a vibrational dipole moment for the nu(sub 12) fundamental has been derived. Observed and calculated spectra covering the region from 740 cm(exp -1) and to 910 cm(exp -1) are presented. A compilation of transition frequencies, line intensities, and lower state energies are included for general use in the astronomical community.

Weber, Mark↗

NASA NTRS2003

High Resolution Spectroscopy to Support Atmospheric Measurements

Spectroscopic parameters (such as line position, intensity, broadening and shifting coefficients and their temperature dependences, line mixing coefficients etc.) for various molecular species of atmospheric interest are determined. In order to achieve these results, infrared spectra of several molecular bands are obtained using high-resolution recording instruments such as tunable diode laser spectrometer and Fourier transform spectrometers. Using sophisticated analysis routines (Multispectrum nonlinear least squares technique) these high-resolution infrared spectra are processed to determine the various spectral line parameters that are cited above. Spectra were taken using the McMath-Pierce Fourier transform spectrometer (FTS) at the National Solar Observatory on Kitt Peak, Arizona as well as the Bruker FTS at the Pacific Northwest National Laboratory (PNNL) at Richland, Washington. Most of the spectra are acquired not only at room temperature, but also at several different cold temperatures. This procedure is necessary to study the variation of the spectral line parameters as a function of temperature in order to simulate the Earth's and other planetary atmospheric environments. Depending upon the strength or weakness of the various bands recorded and analyzed, the length(s) of the absorption cells in which the gas samples under study are kept varied from a few centimeters up to several meters and the sample temperatures varied from approximately +30 C to -63 C. Research on several infrared bands of various molecular species and their isotopomers are undertaken. Those studies are briefly described.

Venkataraman, Malathy Devi↗

NASA NTRS2010

Rayleigh Scattering Measurements Using a Tunable Liquid Crystal Fabry-Perot Interferometer

Spectroscopic Rayleigh scattering is an established flow diagnostic that has the ability to provide simultaneous density, velocity, and temperature measurements. The Fabry-Perot interferometer or etalon is a commonly employed instrument for resolving the spectrum of molecular Rayleigh scattered light for the purpose of evaluating these flow properties. This paper investigates the use of a tunable liquid crystal (LC) Fabry-Perot etalon in Rayleigh scattering experiments at NASA Glenn Research Center. The LC etalon provides a robust interferometry system that can be tuned rapidly by adjusting the voltage applied to the liquid crystal interface. Tuning the interferometer is often necessary to control the physical locations of the concentric interference fringes when Rayleigh light is imaged through the LC etalon. The LC etalon diagnostic system was tested in a 1-cm diameter nozzle flow in two different scattering configurations to evaluate its usefulness for Rayleigh measurements compared to a traditional non-tunable fused silica Fabry-Perot etalon.

Mielke-Fagan, Amy F.↗

NASA NTRS1983

Laser optogalvanic spectroscopy of molecules

In laser optogalvanic (LOG) spectroscopy, a tunable laser is used to probe the spectral characteristics of atomic or molecular species within an electrical discharge in a low pressure gas. Optogalvanic signals arise when the impedance of the discharge changes in response to the absorption of laser radiation. The technique may, therefore, be referred to as impedance spectroscopy. This change in impedance may be monitored as a change in the voltage across the discharge tube. LOG spectra are recorded by scanning the wavelength of a chopped CW dye laser while monitoring the discharge voltage with a lock-in amplifier. LOG signals are obtained if the laser wavelength matches a transition in a species present in the discharge (or flame), and if the absorption of energy in the laser beam alters the impedance of the discharge. Infrared LOG spectroscopy of molecules has been demonstrated and may prove to be the most productive application in the field of optogalvanic techniques.

Webster, C. R.↗

NASA NTRS1985

Generation of tunable laser sidebands in the far-infrared region

In recent years, several techniques have been developed for the generation of tunable coherent radiation at submillimeter and far-infrared (FIR) wavelengths. The harmonic generation of conventional microwave sources has made it possible to produce spectrometers capable of continuous operation to above 1000 GHz. However, the sensitivity of such instruments drops rapidly with frequency. For this reason, a great deal of attention is given to laser-based methods, which could cover the entire FIR region. Tunable FIR radiation (approximately 100 nW) has been produced by mixing FIR molecular lasers and conventional microwave sources in both open and closed mixer mounts. The present investigation is concerned with improvements in this approach. These improvements provide approximately thirty times more output power than previous results.

Farhoomand, J.↗

NASA NTRS1996

Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

McBee, Joshua↗

NASA NTRS1977

Atmospheric lidar research applying to H2O, O2 and aerosols

Experimental research on a near infrared tunable dye laser was reported, and theoretical simulations were presented for various lidar configurations. The visible and nearinfrared wavelengths considered were suitable for observations of aerosols, water vapor, molecular oxygen pressure and temperature in the troposphere and above. The first phase of development work was described on a ruby pumped, tunable dye laser for the wavelength region 715 to 740 nanometers. Lidar simulations were summarized for measurements of H2O and for two color lidar observations of aerosols in the atmosphere.

Mcilrath, T. J.↗

NASA NTRS2012

Compact Two-step Laser Time-of-Flight Mass Spectrometer for in Situ Analyses of Aromatic Organics on Planetary Missions

RATIONALE A miniature time-of-flight mass spectrometer has been adapted to demonstrate two-step laser desorption-ionization (LOI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional laser ionization-desorption, in order to produce low-fragmentation conditions for complex organic analytes. Tuning UV ionization laser energy allowed control ofthe degree of fragmentation, which may enable better identification of constituent species. METHODS A reflectron time-of-flight mass spectrometer prototype measuring 20 cm in length was adapted to a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. Instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. RESULTS L2MS analysis of a model PAH standard, pyrene, has been demonstrated, including parent mass identification and the onset o(tunable fragmentation as a function of ionizing laser energy. Mass resolution m/llm = 380 at full width at half-maximum was achieved which is notable for gas-phase ionization of desorbed neutrals in a highly-compact mass analyzer. CONCLUSIONS Achieving two-step laser mass spectrometry (L2MS) in a highly-miniature instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of parent and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. Selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is presented.

Getty, Stephanie↗

NASA NTRS1978

Deuterated ammonia toward the Orion Nebula

The detection of transitions in NH2D at 85926.2 and 110153.4 MHz from the Orion molecular cloud is reported. An 11-m radio telescope with an 80-120 GHz cooled Cassegrain receiver and a tunable quasi-optical rejection filter was used in the investigations. Equations of statistical equilibrium for the lowest 34 energy levels of NH2D were solved. It seems unlikely that the observed lines arise in the very extended CO cloud. However, they could originate either in the molecular 'ridge' or the unresolved (Kleinmann-Low) core of the cloud or both. A column density of about 50 trillion/sq cm is deduced. The NH2D spectra, with 1 MHz resolution, are shown in a graph. Using previously reported column densities for NH3, a value of 0.05 with an estimated maximum uncertainty factor of 10 is found for the ratio NH2D/NH3.

Rodriguez Kuiper, E. N.↗