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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Arylethynyl Substituted 9,lO-Anthraquinones: Tunable Stokes Shifts by Substitution and Solvent Polarity

2-Arylethynyl- and 2,6- and 2,7-diarylethynyl-substituted 9,lO-anthraquinones were synthesized via Sonogashira coupling reactions of 2-bromo-, 2,6-dibromo-, and 2,7-dibromo-9,10- anthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants with different slopes for electron donors and electron acceptors. ABI compounds are photoluminescent both in solution (quantum yields of emission <= 6 %), and as solids. The emission spectra have the characteristics of charge-transfer bands with large Stokes shifts (100-250 nm). The charge-transfer character of the emitting state is supported by large dipole moment differences between the ground and the excited state as concluded on the basis of molecular modeling and Lippert-Mataga correlations of the Stokes shifts with solvent polarity. Maximum Stokes shifts are attained by both electron-donating and -withdrawing groups. This is explained by a destabilization of the HOMO by electron donors and a stabilization of the LUMO by electron acceptors. X-ray crystallographic analysis of, for example, 2,7-bisphenylethynfl- 9,lO-anthraquinone reveals a monoclinic P21In space group and no indication for pi-overlap that would promote quenching, thus explaining emission from the solid state. Representative reduced forms of the title compounds were isolated as stable acetates of the corresponding dihydrs-9,10- anthraquinones. The emission of these compounds is blue-shifted relative to the parent oxidized forms and is attributed to internal transitions in the dihydro-9,lO-anthraquinone core.

Yang, Jinhua↗
NASA NTRS2004

Coronagraphic Notch Filter for Raman Spectroscopy

A modified coronagraph has been proposed as a prototype of improved notch filters in Raman spectrometers. Coronagraphic notch filters could offer alternatives to both (1) the large and expensive double or triple monochromators in older Raman spectrometers and (2) holographic notch filters, which are less expensive but are subject to environmental degradation as well as to limitations of geometry and spectral range. Measurement of a Raman spectrum is an exercise in measuring and resolving faint spectral lines close to a bright peak: In Raman spectroscopy, a monochromatic beam of light (the pump beam) excites a sample of material that one seeks to analyze. The pump beam generates a small flux of scattered light at wavelengths slightly greater than that of the pump beam. The shift in wavelength of the scattered light from the pump wavelength is known in the art as the Stokes shift. Typically, the flux of scattered light is of the order of 10 7 that of the pump beam and the Stokes shift lies in the wave-number range of 100 to 3,000 cm 1. A notch filter can be used to suppress the pump-beam spectral peak while passing the nearby faint Raman spectral lines. The basic principles of design and operation of a coronagraph offer an opportunity for engineering the spectral transmittance of the optics in a Raman spectrometer. A classical coronagraph may be understood as two imaging systems placed end to end, such that the first system forms an intermediate real image of a nominally infinitely distant object and the second system forms a final real image of the intermediate real image. If the light incident on the first telescope is collimated, then the intermediate image is a point-spread function (PSF). If an appropriately tailored occulting spot (e.g., a Gaussian-apodized spot with maximum absorption on axis) is placed on the intermediate image plane, then the instrument inhibits transmission of light from an on-axis source. However, the PSFs of off-axis light sources are formed off axis - that is, away from the occulting spot - so that they become refocused onto the final image plane.

Cohen, David↗
NASA NTRS1990

Stimulated Raman-scattering threshold behavior of binary mixture micrometer-sized droplets

Stimulated Raman scattering (SRS) from binary liquid mixture micrometer-sized droplets irradiated by nanosecond laser pulses exhibits previously unreported features. SRS emission at wavelength shifts corresponding to combination frequencies of the individual component Stokes shifts are observed in droplets but not in bulk mixtures. Furthermore, droplet SRS thresholds are determined by component refractive indices and concentrations, in contrast to bulk thresholds, for which self-focusing likely plays a dominant role.

Biswas, Abhijit↗
NASA NTRS2003

Synthesis and Photoluminescent Properties of Arylethynyl substituted 9,10-Anthraquinones

A series of arylethynyl substituted anthraquinones were synthesized via Sonogashira coupling reactions of 2,7- dibromo-, 2,6-dibromo- and 2-bromoanthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants for electron donating and electron withdrawing groups separately. All compounds are photoluminescent both in solution (quantum yield of emission approximately 2%) and as solids. X-ray crystallographic characterization of 2,7-bisphenylethynyl anthraquinone indicates a monoclinic p2(l/n) space group and no indication for pi-overlap that would promote self-quenching. The emission maxima are red- shifted by both electron donating and electron withdrawing groups alike. The Stokes shifts of all compounds are significant and are correlated to the electronic properties of the substituents. The reduced forms of these compounds are also photoluminescent and the emission originates from the dihydroanthraquinone core.

Yang, Jin-Hua↗
NASA NTRS1981

CARS measurement of velocity in a supersonic jet

It is shown that CW CARS can be used to measure velocity in supersonic flows. The accuracy with which the Doppler shift can be measured is determined through the drift in the laser frequencies. In the experiment described here, it is found that a laser drift error of 10 MHz during the recording of a spectrum would limit the velocity resolution to 34 m/s. It is noted that improved frequency stabilization of the laser sources could lead to a velocity measurement accuracy of several m/s. In the experiment, a 4-W single axial mode argon ion laser is the pump source, and the Stokes-shifted frequency is generated by a 100-mW tunable dye laser.

Gustafson, E. K.↗
NASA NTRS1979

Investigations of coherent anti-Stokes Raman spectroscopy /CARS/ for combustion diagnostics

Investigations of coherent anti-Stokes Raman spectroscopy (CARS) in a variety of flames are presented. Thermometry has received the primary emphasis in these studies, but species spectral and sensitivity studies will also be described. CARS is generated by mixing a 10 pps, frequency-doubled neodymium 'pump' laser with a spectrally broadband, laser-pumped, Stokes-shifted dye laser. This approach obviates the requirement to frequency scan the dye laser and generates the entire CARS spectrum with each pulse permitting, in principle, instantaneous measurements of medium properties. CARS spectra of N2, CO, O2, H2O, CO2 and CH4 in flames will be presented. In general these spectra exhibit very good agreement with computer synthesized spectra and permit measurements of temperature and species concentration. To illustrate the applicability of CARS to practical combustion diagnostics, CARS signatures from N2 have been employed to map the temperature field throughout a small, luminous, highly sooting propane diffusion flame

Eckbreth, A. C.↗
NASA NTRS1998

Stimulated Raman amplification, oscillation, and linewidth in barium nitrate

Measurements of Raman gain in a Ba(NO3)2 crystal are reported at 532 nm using a Raman oscillator/amplifier arrangement for differential absorption lidar measurements of ozone. The experimentally determined gain coefficient will be compared with theoretical results. The effect of single and multi-longitudinal mode pumping upon the amplification process will be discussed. Measurement of the Raman linewidth for 1st 2nd and 3d stokes shifts arc presented.

McCray, Christopher J.↗
NASA NTRS2003

Measurement and Simulation of Spontaneous Raman Scattering Spectra in High-Pressure, Fuel-Rich H2-Air Flames

Rotational vibrational spontaneous Raman spectra (SRS) of H2, N2, and H2O have been measured in H2-air flames at pressures up to 30 atm as a first stem towards establishing a comprehensive Raman spectral database for temperatures and species in high-pressure combustion. A newly developed high-pressure burner facility provides steady, reproducible flames with a high degree of flow precision. We have obtained an initial set of measurements that indicate the spectra are of sufficient quality in terms of spectral resolution, wavelength coverage, and signal-to-noise ratio for use in future reference standards. The fully resolved Stokes and anti-Stokes shifted SRS spectra were collected in the visible wavelength range (400-700 nm) using pulse-stretched 532 nm excitation and a non-intensified CCD spectrograph with a high-speed shutter. Reasonable temperatures were determined via the intensity distribution of rotational H2 lines at stoichiometry and fuel-rich conditions. Theoretical Raman spectra of H2 were computed using a semi-classical harmonic-oscillator model with recent pressure broadening data and were compared with experimental results. The data and simulation indicated that high-J rotational lines of H2 might interfere with the N2 vibrational Q-branch lines, and this could lead to errors in N2-Raman thermometry based on the line-fitting method. From a comparison of N2 Q-branch spectra in lean H2 low-pressure (1.2 atm) and high-pressure (30 atm) flames, we found no significant line-narrowing or -broadening effects at the current spectrometer resolution of 0.04 nm.

Kojima, Jun↗
NASA NTRS1973

SO2 Spectroscopy with A Tunable UV Laser

A portion of the fluorescence spectrum of SO2 has been studied using a narrow wavelength doubled dye laser as the exciting source. One purpose of this study is to evaluate the use of SO2 resonance re-emission as a probe of SO2 in the atmosphere. When the SO2 is excited by light at 300.2 nm, for example, a strong reemission peak is observed which is Stokes-shifted from the incident light wavelength by the usual Raman shift (the VI symmetric vibration frequency 1150.5/cm ). The intensity of this peak is sensitive to small changes (.01 nm) in the incident wavelength. Measurements of the N2 quenching and self quenching of this re-emission have been obtained. Preliminary analysis of this data indicates that the quenching is weak but not negligible. The dye laser in our system is pumped by a pulsed N2 laser. Tuning 'and spectral narrowing are accomplished using a telescope-echelle grating combination. In a high power configuration the resulting pulses have a spectral width of about 5 x 10(exp -3) nm and a time duration of about 6 nsec. The echelle grating is rotated by a digital stepping motor, such that each step shifts the wavelength by 6 x 10(exp -4) nm. In addition to the tunable, narrow wavelength uv source and spectral analysis of the consequent re-emission, the system also provides time resolution of the re-emitted light to 6 nsec resolution. This capability is being used to study the lifetime of low pressure S02 fluorescence at different wavelengths and pressures.

Morey, W. W.↗
NASA NTRS1989

Comment on linewidths and shifts in the Stokes-Raman Q branch of D2 in He

Collision-induced widths and shifts for Raman Q-branch transitions of D2 in He were calculated from S matrices obtained with converged close coupling scattering calculations on an accurate theoretical interaction potential. Results agree well with experimental values. Discrepancies between experimental line shifts and theoretical values from an earlier study (Blackmore et al., 1988) are traced to a computational error in that work. The effects of vibrational inelasticity and of centrifugal distortion on energy levels and on potential matrix elements, all of which were ignored in the earlier study, are explicitly considered here and found to be small.

Green, Sheldon↗
NASA NTRS1993

Stokes seeding of a Raman shifting cell for use in RELIEF velocimetry

The seeding of a high pressure oxygen, stimulated vibrational Raman shifting cell with a small amount of first-order Stokes radiation is described. The output radiation from this cell was used to vibrationally excite oxygen in a low-speed air flow, and that vibrationally-excited oxygen was detected using laser-induced fluorescence imaging (the RELIEF technique). Comparison of collected fluorescence signal with and without first-order Stokes seeding showed an enhancement by more than a factor of three when the seed was used.

Diskin, Glenn S.↗
NASA NTRS2003

Proposal for Testing and Validation of Vacuum Ultra-Violet Atomic Laser-Induced Fluorescence as a Method to Analyze Carbon Grid Erosion in Ion Thrusters

Previous investigation under award NAG3-25 10 sought to determine the best method of LIF to determine the carbon density in a thruster plume. Initial reports from other groups were ambiguous as to the number of carbon clusters that might be present in the plume of a thruster. Carbon clusters would certainly affect the ability to LIF; if they were the dominant species, then perhaps the LIF method should target clusters. The results of quadrupole mass spectroscopy on sputtered carbon determined that minimal numbers of clusters were sputtered from graphite under impact from keV Krypton. There were some investigations in the keV range by other groups that hinted at clusters, but at the time the proposal was presented to NASA, there was no data from low-energy sputtering available. Thus, the proposal sought to develop a method to characterize the population only of atoms sputtered from a graphite target in a test cell. Most of the ground work had been established by the previous two years of investigation. The proposal covering 2003 sought to develop an anti-Stokes Raman shifting cell to generate VUW light and test this cell on two different laser systems, ArF and YAG- pumped dye. The second goal was to measure the lowest detectable amounts of carbon atoms by 156.1 nm and 165.7 nm LIF. If equipment was functioning properly, it was expected that these goals would be met easily during the timeframe of the proposal, and that is the reason only modest funding was requested. The PI was only funded at half- time by Glenn during the summer months. All other work time was paid for by Whitworth College. The college also funded a student, Charles Shawley, who worked on the project during the spring.

Stevens, Richard↗
NASA NTRS1999

Time-Shifted Boundary Conditions Used for Navier-Stokes Aeroelastic Solver

Under the Advanced Subsonic Technology (AST) Program, an aeroelastic analysis code (TURBO-AE) based on Navier-Stokes equations is currently under development at NASA Lewis Research Center s Machine Dynamics Branch. For a blade row, aeroelastic instability can occur in any of the possible interblade phase angles (IBPA s). Analyzing small IBPA s is very computationally expensive because a large number of blade passages must be simulated. To reduce the computational cost of these analyses, we used time shifted, or phase-lagged, boundary conditions in the TURBO-AE code. These conditions can be used to reduce the computational domain to a single blade passage by requiring the boundary conditions across the passage to be lagged depending on the IBPA being analyzed. The time-shifted boundary conditions currently implemented are based on the direct-store method. This method requires large amounts of data to be stored over a period of the oscillation cycle. On CRAY computers this is not a major problem because solid-state devices can be used for fast input and output to read and write the data onto a disk instead of storing it in core memory.

Srivastava, Rakesh↗
NASA NTRS2004

Transitional Bubble in Periodic Flow Phase Shift

One particular characteristic observed in unsteady shear layers is the phase shift relative to the main flow. In attached boundary layers this will have an effect both on the instantaneous skin friction and heat transfer. In separation bubbles the contribution to the drag is dominated by the pressure distribution. However, the most significant effect appears to be the phase shift on the transition process. Unsteady transition behaviour may determine the bursting of the bubble resulting in an un-recoverable full separation. An early analysis of the phase shift was performed by Stokes for the incompressible boundary layer of an oscillating wall and an oscillating main flow. An amplitude overshoot within the shear layer as well as a phase shift were observed that can be attributed to the relatively slow diffusion of viscous stresses compared to the fast change of pressure. Experiments in a low speed facility with the boundary layer of a flat plate were evaluated in respect to phase shift. A pressure distribution similar to that on the suction surface of a turbomachinery aerofoil was superimposed generating a typical transitional separation bubble. A periodically unsteady main flow in the suction type wind tunnel was introduced via a rotating flap downstream of the test section. The experiments covered a range of the three similarity parameters of momentum-loss-thickness Reynolds-number of 92 to 226 and Strouhal-number (reduced frequency) of 0.0001 to 0.0004 at the separation point, and an amplitude range up to 19 %. The free stream turbulence level was less than 1% .Upstream of the separation point the phase shift in the laminar boundary layer does not appear to be affected significantly bay either of the three parameters. The trend perpendicular to the wall is similar to the Stokes analysis. The problem scales well with the wave velocity introduced by Stokes, however, the lag of the main flow near the wall is less than indicated analytically. The separation point comes closest to the Stokes analysis but the phase is still 20 degrees lower at the wall.

Talan, M.↗
NASA NTRS1987

Mid infrared LHS system packaging using flexible waveguides

As mid IR fiber optic systems are rapidly approaching a reality, so is the feasibility of fiber optic laser heterodyne systems. Laser heterodyne spectroscopy for high resolution monitoring of atmospheric gaseous pollutants is necessarily in the mid IR, the region in which the absorption signature of gaseous species is most prominent. It so happens that the lowest theoretical loss due to Rayleigh-Brillouin scattering also lies in the mid IR. Prospects of highly efficient laser heterodyne systems are thus very good. Such fibers are now beginning to be commercially available, and a test program is being conducted for such fibers with ambient temperature ranging from cryogenic to above room, and stringest mechanical flexibility requirements. Preliminary results are encouraging. A program is being started to explore the possibility of mid IR fiber optic device applications, by taking advantage of this phonon rich region. The potential long interaction length in fibers coupled with predicted extremely low losses point to stimulated Brillouin scattering based devices in the mW range. The generation of backscattered sBs at low laser powers is significant not only as an ultimate power limiting factor for laser transmission in fibers in the mid IR, but also the presence of frequency-shifted multiple order sBs Stokes and antiStokes lines will certainly have severe effect on the laser beats crucial in high resolution heterodyne spectroscopy.

Yu, Chung↗
NASA NTRS1984

Wall mass transfer and pressure gradient effects on turbulent skin friction

The effects of mass injection and pressure gradients on the drag of surfaces were studied theoretically with the aid of boundary-layer and Navier-Stokes codes. The present investigation is concerned with the effects of spatially varying the injection in the case of flat-plate drag. Effects of suction and injection on wavy wall surfaces are also explored. Calculations were performed for 1.2 m long surfaces, one flat and the other sinusoidal with a wavelength of 30.5 cm. Attention is given to the study of the effect of various spatial blowing variations on flat-plate skin friction reduction, local skin friction coefficient calculated by finite difference boundary-layer code and Navier-Stokes code, and the effect of phase-shifting sinusoidal mass transfer on the drag of a sinusoidal surface.

Watson, R. D.↗
NASA NTRS1988

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Herring, G. C.↗