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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.

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At least 19 records

Use of an Internal Mercury-Argon Lamp for the Calibration of Raman Frequency in Large Raman Images of Astromaterials

Raman imaging is an emerging tool for the analysis of meteorites, as it is capable of describing mineralogy, carbon composition/speciation, and crystal orientation all within a petrographic context. Adequately examining the heterogeneous composition of a meteorite, while maintaining low laser powers needed to prevent damage to meteorite mineralogy and organics, often requires the collection of large Raman images with long collection times on the timescale of days. However, the frequency calibration of the Raman instrument/spectrometer drifts on long timescales resulting in low frequency precision for the Raman spectra comprising a large Raman image. This decrease in frequency precision can compromise the analysis of geological markers that can provide important information on a meteorite sample. We examine, in detail, the change in bandwidth and frequency of the Raman bands and Hg-Ar emission lines in our Raman images as a function of time and laboratory temperature. To overcome the drift in calibration, we utilize a commercial WITec Raman instrument with an internal Hg-Ar calibration lamp to individually calibrate each spectrum in the Raman image. Our instrument, known as “Ratatoskr”, uses a beam splitter in place of the customary mirror to facilitate collection of Hg-Ar calibration lines concurrent with Raman spectra. We show that using the internal calibration we can improve the frequency precision for the spectra in our Raman images from ~±0.15 cm(exp -1) to ~±0.05 cm(exp -1) for Raman spectra collected over multiple days. This is important as it improves measurements of mineral chemistry, latent strain, and other features that are dependent upon accurate peak position determination. We also examine the spectral signal-to-noise ratio needed to minimize the frequency error when fitting bands to Gaussian/Lorentzian profiles. We then use our results to suggest a general method for calibrating the frequency of Raman spectra in large Raman images.

Jakubek, Ryan S.↗

Use of an Internal Mercury-Argon Lamp for the Calibration of Raman Frequency in Large Raman Images of Astromaterials

Raman imaging is an emerging tool for the analysis of meteorites, as it is capable of describing the mineralogy and organics within a petrographic context. Adequately examining the heterogeneous composition of a meteorite often requires the collection of large Raman images with long collection times on the time-scale of days. However, the frequency calibration of the Raman instrument/spectrometer drifts on long timescales resulting in low frequency precision for the Raman spectra comprising a large Raman image. Here we utilize a Hg-Ar calibration lamp integrated into our Raman microscope to calibrate the Raman spectra within a Raman image. We characterize this method of calibration in detail.

Ryan S. Jakubek↗

Fine Structure of the Low-Frequency Raman Phonon Bands of Single-Wall Carbon Nanotubes

The Raman spectra of singled-wall carbon nanotubes (SWNT) produced by laser and are process were studied between 5 and 500 kappa. The line width vs. temperature dependence of the low-frequency Raman bands between 150 and 200/ cm deviates from that expected for phonon decay through phonon-phonon scattering mechanism. The experimental results and their analysis provided convincing evidence that each of the low-frequency Raman lines is a superposition of several narrower Raman lines corresponding to tubes of nearly the same diameter. The application of Raman spectroscopy to probe the distribution of SWNT by both diameter and chirality is discussed.

Iliev, M. N.↗

Plume Characterization of a Laboratory Model 22 N GPIM Thruster via High-Frequency Raman Spectroscopy

The Green Propellant Infusion Mission (GPIM) will demonstrate the capability of a green propulsion system, specifically, one using the monopropellant, AF-M315E. One of the risks identified for GPIM is potential contamination of sensitive areas of the spacecraft from the effluents in the plumes of AF-M315E thrusters. Plume characterization of a laboratory-model 22 N thruster via optical diagnostics was conducted at NASA GRC in a space-simulated environment. A high-frequency pulsed laser was coupled with an electron-multiplied ICCD camera to perform Raman spectroscopy in the near-field, low-pressure plume. The Raman data yielded plume constituents and temperatures over a range of thruster chamber pressures and as a function of thruster (catalyst) operating time. Schlieren images of the near-field plume enabled calculation of plume velocities and revealed general plume structure of the otherwise invisible plume. The measured velocities are compared to those predicted by a two-dimensional, kinetic model. Trends in data and numerical results are presented from catalyst mid-life to end-of-life. The results of this investigation were coupled with the Raman and Schlieren data to provide an anchor for plume impingement analysis presented in a companion paper. The results of both analyses will be used to improve understanding of the nature of AF-M315E plumes and their impacts to GPIM and other future missions.

Raman Spectroscopy↗

Analysis of torsional spectra of molecules with two internal C3v rotors. II - Far infrared and low frequency Raman spectra of dimethylether isotopes

The torsional far infrared and Raman spectra of gaseous CH3OCH3, CD3OCH3, and CD3OCD3 are presented. They are analyzed using a computer program which is based on the results of an extensive investigation of the isometric groups and of the symmetry groups of the rotation-internal rotation Hamiltonians of a series of semirigid two-top models. Four or more Fourier coefficients of the potential functions in two variables could be determined for each isotope. Strong evidence was found for Fermi-resonance-type interactions with the COC bending mode.

Groner, P.↗

Development of a two photon/laser induced fluorescence technique for the detection of atmospheric OH radicals

The development of a new mid-IR laser source was the primary goal. Backward propagating stimulated D2 Raman frequency down conversion of a commercially available 1.06 micron Nd:YAG laser was shown to generate an efficient source of 1.56 micron radiation with near diffraction limited beam quality. The efficient generation of a 2.9 micron laser source was also achieved using backward propagating CH4 Raman frequency down conversion of the 1.56 micron pump. Slightly higher efficiencies were obtained for frequency down conversion of the 1.06 micron Nd:YAG using the H2 Raman shift yielding a near diffraction limited source in the 200 mJ range at 1.9 micron. Similar conversion efficiencies are anticipated as a result of extending the wavelength coverage of recently available Ti:sapphire pulse laser to not only cover the 740 to 860 nm fundamental wavelength range but also the .95 to 1.15 and 1.06 to 1.33 micron range using D2 and H2, respectively. The anticipated sensitivity of a TP-LIF OH sensor using this mid-IR source would give signal limited detection of 1.4 x 10(exp 5) OH/cu cm under boundary layer conditions and 5.5 x 10(exp 4) OH/cu cm under free troposphere sampling conditions for a five minute signal integration period. This level of performance coupled with the techniques non-perturbing nature and freedom from both interferences and background would allow reliable tropospheric OH measurement to be obtained under virtually any ambient condition of current interest, including interstitial and sampling.

Bradshaw, John↗

Thermodynamic measurements in a high pressure hydrogen-oxygen flame using Raman scattering from a broadband excimer laser

Raman scattering is an inelastic molecular scattering process in which incident radiation is reemitted at a fixed change in frequency. Raman spectroscopy can be used to measure the number density and temperature of the irradiated species. The strength of the Raman signal is inversely proportional to the wavelength raised to the fourth power. Consequently, high signal to noise ratios are obtained by using ultraviolet (UV) excitation sources. Using UV sources for Raman Spectroscopy in flames is complicated by the fact that some of the primary constituents in hydrogen-oxygen combustion absorb and reemit light in the UV and these fluorescence processes interfere with the Raman signals. This problem has been handled in atmospheric pressure flames in some instances by using a narrowband tunable excimer laser as a source. This allows for detuning from absorption transitions and the elimination of interfering fluorescence signals at the Raman wavelengths. This approach works well in the atmospheric pressure flame; however, it has two important disadvantages. First, injection-locked narrowband tunable excimer lasers are very expensive. More importantly, however, is the fact that at the high pressures characteristic of rocket engine combustion chambers, the absorption transitions are broadened making it difficult to tune to a spectral location at which substantial absorption would not occur. The approach taken in this work is to separate the Raman signal from the fluorescence background by taking advantage of the fact that Raman signal has nonisotropic polarization characteristics while the fluorescence signals are unpolarized. Specifically, for scattering at right angles to the excitation beam path, the Raman signal is completely polarized. The Raman signal is separated from the fluorescence background by collecting both horizontally and vertically polarized signals separately. One of the polarizations has both the Raman signal and the fluorescence background while the other has only the fluorescence signal. The Raman scatter is the difference between the signals. By choosing an appropriate optical setup, both signals can be obtained simultaneously with the same monochromator; hence, time resolved measurements are possible using this approach.

Hartfield, Roy, Jr.↗

Synthesis, Characterization, and Theoretical Considerations of 1,2-bis(oxyamino)ethane Salts

The synthesis, characterization, theoretical calculations, and safety studies of energetic salts of 1,2- bis(oxyamino) ethane, (H2N-O-CH2-CH2-O-NH2), were carried out. The salts were characterized by vibrational (infrared, Raman), multinuclear nmr studies (1H, 13C), differential scanning calorimetry (DSC); elemental analysis; and initial safety testing (impact and friction sensitivity) . Theoretical calculations on the neutral, monoprotonated, and doubly protonated species of ethylene bisoxyamine were carried out using xxxx level of theory for the lowest energy structure and these theoretical results compared with the experimentally observed bond distances and vibrational (ir, Raman) frequency values. The single crystal X-ray diffraction study was carried out on the mono-perchlorate salt revealing a high degree of hydrogen bonding with an unexpected structure.

1-2-BIS- (OXYAMINO)ETHANE SALTS↗

Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

This work focused on understanding the effects of arbitrary transverse and longitudinal relaxation rates on the susceptibilities of coherently driven three-level systems. The approximation of a single relaxation rate often made in previous work is strongly invalidated by the variation in the spontaneous emission lifetime between various atomic level pairs in systems such as cesium. It is of great importance to the problem of nonlinear infrared generation to determine the dependence of both real and imaginary susceptibility on relaxation rates. The imaginary susceptibility on the pump transition determines the absorption of pump photons and the imaginary susceptibility on the laser transition determines the spectral dependence of the gain. This is of particular importance for pure Raman emission (i.e., absorption at linecenter of the gain transition) as it determines the tunability characteristics we are aiming to predict. The real susceptibility is important when cavities are used at the signal field as this will determine the loaded resonance of the Raman oscillator. Researchers show that in some cases which result from having different relaxation rates mode splitting may result, allowing more than one frequency to have the same Raman wavelength, possibly resulting in a temporal instability.

Lawandy, N. M.↗

Theoretical studies of Resonance Enhance Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

It is well known that the presence of a real atomic level which is nearly resonant with the pump field can greatly enhance the Raman emission cross section. In order to accurately calculate the Raman gain in systems where resonance enhancement plays a dominant role, expressions for the pump and signal susceptibilities must be derived. These expressions should be valid for arbitrary field strengths in order to allow for pump and signal saturation. In addition, the theory should allow for arbitrary longitudinal and transverse relaxation rates. This latter point is extremely vital for three level atomic systems such as the alkali earth metals since they do not have population reservoirs and can have widely varying spontaneous lifetimes on the three pertinent transitions. Moreover, the dephasing rates are strong functions of electron states and are therefore also different for the three coupled pairs of levels. These considerations are not as important when molecular systems are concerned since the large reservoir of rotational states serve to produce essentially equal longitudinal recovery rates for the population of the three levels. The three level system with three arbitrary longitudinal and transverse relaxation rates was solved. There is no need for setting either pair of rates equal and the expressions are valid for arbitrarily strong fields.

Lawandy, N. M.↗

Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelength in cesium vapor

The third phase of research will focus on the propagation and energy extraction of the pump and SERS beams in a variety of configurations including oscillator structures. In order to address these questions a numerical code capable of allowing for saturation and full transverse beam evolution is required. The method proposed is based on a discretized propagation energy extraction model which uses a Kirchoff integral propagator coupled to the three level Raman model already developed. The model will have the resolution required by diffraction limits and will use the previous density matrix results in the adiabatic following limit. Owing to its large computational requirements, such a code must be implemented on a vector array processor. One code on the Cyber is being tested by using previously understood two-level laser models as guidelines for interpreting the results. Two tests were implemented: the evolution of modes in a passive resonator and the evolution of a stable state of the adiabatically eliminated laser equations. These results show mode shapes and diffraction losses for the first case and relaxation oscillations for the second one. Finally, in order to clarify the computing methodology used to exploit the speed of the Cyber's computational speed, the time it takes to perform both of the computations previously mentioned to run on the Cyber and VAX 730 must be measured. Also included is a short description of the current laser model (CAVITY.FOR) and a flow chart of the test computations.

Lawandy, Nabil M.↗

Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency-doubled Alexandrite laser wavelength in cesium vapor

The solutions for the imaginary susceptibility of the Raman field transition with arbitrary relaxation rates and field strengths are examined for three different sets of relaxation rates. These rates correspond to: (1) Far Infrared (FIR) Raman lasers in the diabatic collision regime without consideration of coupled population decay in a closed system, (2) Raman FIR lasers in the diabatic collision regime with coupled population conserving decay, and (3) IR Raman gain in cesium vapor. The model is further expanded to include Doppler broadening and used to predict the peak gain as a function of detuning for a frequency doubled Alexandrite laser-pumped cesium vapor gain cell.

Lawandy, Nabil M.↗

Local Intensity Enhancements in Spherical Microcavities: Implications for Photonic Chemical and Biological Sensors

In this report, we summarize recent findings regarding the use spherical microcavities in the amplification of light that is inelastically scattered by either fluorescent or Raman-active molecules. This discussion will focus on Raman scattering, with the understanding that analogous processes apply to fluorescence. Raman spectra can be generated through the use of a very strong light source that stimulates inelastic light scattering by molecules, with the scattering occurring at wavelengths shifted from that of the source and being most prominent at shifts associated with the molecules natural vibrational frequencies. The Raman signal can be greatly enhanced by exposing a molecule to the intense electric fields that arise near surfaces (typically of gold or silver) exhibiting nanoscale roughness. This is known as surface-enhanced Raman scattering (SERS). SERS typically produces gain factors of 103 - 106, but under special conditions, factors of 1010 - 1014 have been achieved.

Fuller, Kirk A.↗

Diagnostics of silane and germane radio frequency plasmas by coherent anti-Stokes Raman spectroscopy

In situ plasma diagnostics using coherent anti-Stokes Raman spectroscopy have shown different dissociation characteristics for GeH4 and SiH4 in radio frequency (rf) plasma-enhanced chemical vapor deposition of amorphous silicon germanium alloy (a-SiGe:H) thin films. The GeH4 dissociation rate in rf plasmas is a factor of about 3 larger than that of SiH4. Plasma diagnostics have revealed that the hydrogen dilution of the SiH4 and GeH4 mixed plasma plays a critical role in suppressing the gas phase polymerization and enhancing the GeH4 dissociation.

Perry, Joseph W.↗