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At least 1,009 records · Page 56

Laser-induced fluorescence technique for velocity field measurements in subsonic gas flows

A nonintrusive optical technique is reported for multiple-point velocity measurements in subsonic flows. The technique is based on the detection of fluorescence from a Doppler-shifted absorption line of seeded iodine molecules excited at a laser frequency fixed in the wing of the line. Counterpropagating laser sheets are used to illuminate the flow, in the present case a nitrogen round jet, thereby eliminating the need for an unshifted reference signal. The fluorescence is detected simultaneously at 10,000 points in a plane of the flow using a 100 x 100 element photodiode-array camera. The velocity at each point is computed from four successive camera frames, each recorded with a different beam direction. The measured mean velocities between 5 and 50 m/sec agree well with data from the literature.

Hiller, B.↗

Technology Advancement for Active Remote Sensing of Carbon Dioxide from Space Using the ASCENDS CarbonHawk Experiment Simulator: First Results

The ASCENDS CarbonHawk Experiment Simulator (ACES) is a newly developed lidar developed at NASA Langley Research Center and funded by NASA's Earth Science Technology Office (ESTO) Instrument Incubator Program (IIP) that seeks to advance technologies critical to measuring atmospheric column carbon dioxide (CO2) mixing ratios in support of the NASA Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS) mission. The technology advancements targeted include: (1) increasing the power-aperture product to approach ASCENDS mission requirements by implementing multi-aperture telescopes and multiple co-aligned laser transmitters; (2) incorporating high-efficiency, high-power Erbium-Doped Fiber Amplifiers (EDFAs); (3) developing and incorporating a high-bandwidth, low-noise HgCdTe detector and transimpedence amplifier (TIA) subsystem capable of long-duration autonomous operation on Global Hawk aircraft, and (4) advancing algorithms for cloud and aerosol discrimination. The ACES instrument architecture is being developed for operation on high-altitude aircraft and will be directly scalable to meet the ASCENDS mission requirements. These technologies are critical towards developing not only spaceborne instruments but also their airborne simulators, with lower platform requirements for size, mass, and power, and with improved instrument performance for the ASCENDS mission. ACES transmits five laser beams: three from commercial EDFAs operating near 1.57 microns, and two from the Exelis oxygen (O2) Raman fiber laser amplifier system operating near 1.26 microns. The three EDFAs are capable of transmitting up to 10 watts average optical output power each and are seeded by compact, low noise, stable, narrow-linewidth laser sources stabilized with respect to a CO2 absorption line using a multi-pass gas absorption cell. The Integrated-Path Differential Absorption (IPDA) lidar approach is used at both wavelengths to independently measure the CO2 and O2 column number densities and retrieve the average column CO2 mixing ratio. The ACES receiver uses three fiber-coupled 17.8-cm diameter athermal telescopes. The transmitter assembly consists of five fiber-coupled laser collimators and an associated Risley prism pair for each laser to co-align the outgoing laser beams and to align them with the telescope field of view. The backscattered return signals collected by the three telescopes are combined in a fiber bundle and sent to a single low noise detector. The detector/TIA development has improved the existing detector subsystem by increasing its bandwidth to 4.7 MHz from 500 kHz and increasing the duration of autonomous, service-free operation periods from 4 hours to >24 hours. The new detector subsystem enables the utilization of higher laser modulation rates, which provides greater flexibility for implementing advanced thin-cloud discrimination algorithms as well as improving range-determination resolution and error reduction. The cloud/aerosol discrimination algorithm development by Langley and Exelis features a new suite of algorithms for the minimization/elimination of bias errors in the return signal induced by the presence of intervening thin clouds. Multiple laser modulation schemes are being tested in an effort to significantly mitigate the effects of thin clouds on the retrieved CO2 column amounts. Full instrument development concluded in the spring of 2014. After ground range tests of the instrument, ACES successfully completed six test flights on the Langley Hu-25 aircraft in July, 2014, and recorded data at multiple altitudes over land and ocean surfaces with and without intervening clouds. Preliminary results from these test flights will be presented in this paper.

Obland, Michael D.↗

Nonintrusive fast response oxygen monitoring system for high temperature flows

A new technique has been developed for nonintrusive in situ measurement of oxygen concentration, gas temperature, and flow velocity of the test media in hypersonic wind tunnels. It is based on absorption of near-infrared radiation from inexpensive GaAlAs laser diodes used in optoelectronics industry. It is designed for simultaneous measurements along multiple lines of sight accessed by fiber optics. Molecular oxygen concentration is measured from the magnitude of absorption signals; rotational gas temperature is measured from the intensity ratio of two oxygen absorption lines; and the flow velocity is measured from the Doppler shift of the absorption line positions. This report describes the results of an extensive series of tests of the prototype instrument in laboratory flames emphasizing assessment of the instruments capabilities for quantitative measurement of O2 concentration (mole fraction) and gas temperature.

Oh, Daniel B.↗

Ligand Desorption and Fragmentation in Oleate-Capped CdSe Nanocrystals under High-Intensity Photoexcitation

Semiconductor nanocrystals (NCs) offer prospective use as active optical elements in photovoltaics, light-emitting diodes, lasers, and photocatalysts due to their tunable optical absorption and emission properties, high stability, and scalable solution processing, as well as compatibility with additive manufacturing routes. Over the course of experiments, during device fabrication, or while in use commercially, these materials are often subjected to intense or prolonged electronic excitation and high carrier densities. The influence of such conditions on ligand integrity and binding remains underexplored. Here, in this study, we expose CdSe NCs to laser excitation and monitor changes in oleate that is covalently attached to the NC surface using nuclear magnetic resonance as a function of time and laser intensity. Higher photon doses cause increased rates of ligand loss from the particles, with upward of 50% total ligand desorption measured for the longest, most intense excitation. Surprisingly, for a range of excitation intensities, fragmentation of the oleate is detected and occurs concomitantly with formation of aldehydes, terminal alkenes, H 2 , and water. After illumination, NC size, shape, and bandgap remain constant although low-energy absorption features (Urbach tails) develop in some samples, indicating formation of substantial trap states. The observed reaction chemistry, which here occurs with low photon to chemical conversion efficiency, suggests that ligand reactivity may require examination for improved NC dispersion stability but can also be manipulated to yield desired photocatalytically accessed chemical species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The accuracy of laser tracking

A brief discussion of the actual laser tracking performance of geodetic satellites is followed by a discussion of the errors inherent in the laser system. An estimate is made of the capability expected within the next few years for the tracking of a heliocentric probe. The GEOS 1, GRARR, and GEOS 2 systems are considered. Errors in the tracking of a heliocentric probe are noted. These include errors due to the earth's atmosphere, (beam bending, atmospheric absorption, atmospheric turbulence, and atmospheric distortion of short laser pulses), and errors due to coronal effects.

Blamont, J. E.↗

Analysis of sublimation-cooled coated mirrors in convective and radiative environments.

Analytical solutions were obtained for the thermal response of a transpiration- or sublimation-cooled spherical mirror coating exposed to convective and radiative heating. The solutions allow unlimited spectral detail to be accounted for. Results indicate that transpiration-cooled thick coatings (1 cm) may withstand up to 10 kW/sq cm on a steady basis without excessive temperature rise for quartzlike materials with an internal absorption coefficient of 0.01 per cm. On a transient basis, fluxes up to 20 kW/sq cm can be accommodated for a second (cW laser exposure time), 4 kW/sq cm for 5 sec (planetary entry heating time), and of the order of MW/sq cm for millisecond times (short-duration laser bursts) without transpiration cooling for a material with an absorption coefficient of 0.1 per cm. Proportionately higher fluxes can be accommodated with lower absorption coefficients. Thermal stresses produced by the heat pulse are found to be high but within the strength of the materials. The regime in which meaningful solutions may be obtained is mapped in detail.

Howe, J. T.↗

Intensities and N2 collision-broadening coefficients measured for selected H2O absorption lines between 715 and 732 nm

Intensities and N2 collision-broadening coefficients are measured for 62 water vapor absorption lines between 715 and 732 nm potentially applicable to laser remote sensing of atmospheric water vapor. Absolute line strengths and widths were determined from spectra corrected for instrument resolution, air-path absorption and Lorentz and Doppler broadening for pure water vapor and water vapor-nitrogen mixtures in a multipass absorption cell with a base path length of 25 m (White cell). Line strengths are observed to range from 4 x 10 to the -25th to 4 x 10 to the -23rd kayser/molecule per sq cm, and collision broadening coefficients are found to be approximately equal to 0.1 kayser/atm.

Wilkerson, T. D.↗

100 kHz High-Spectral-Resolution NO-PLIF Measurements for Compressible Flows

In the present work, we use a burst-mode laser and optical parametric oscillator system to perform high-spectral resolution NO-PLIF measurements of an underexpanded jet at a repetition-rate of 100 kHz, with the motivation of multi-parameter measurements of temperature, pressure, and velocity. The laser frequency of the 1064 nm seed laser for the burst-mode laser was scanned during the burst to cover two neighboring absorption line pairs near 226 nm. The peak PLIF signal intensity varies along the axial (z) direction of the underexpanded jet as the laser frequency is scanned, which we attribute to the collisional shift induced by the flow and only revealed due to the narrow linewidth of the laser. A pseudo-Voight fit is applied to the LIF excitation spectra on a pixel-by-pixel basis to measure the spectral position of the peak intensity for the two transition pairs and their amplitude. The spectral position of the peak intensity is used to derive a frequency shift, which is separated into its collisional and Doppler components using the axisymmetric nature of the flow field. The amplitude of the measured peaks is used for two-line rotational thermometry. Challenges for quantitative measurements using such an approach are discussed, including measuring the spatial variations in the energy distribution of the laser sheet at a 100 kHz repetition rate and uncertainty/variability in the step size during the fast frequency scan.

laser induced fluorescence↗

100 kHz High-Spectral-Resolution NO-PLIF Measurements for Compressible Flows

In the present work, we use a burst-mode laser and optical parametric oscillator system to perform high-spectral resolution NO-PLIF measurements of an underexpanded jet at a repetition-rate of 100 kHz, with the motivation of multi-parameter measurements of temperature, pressure, and velocity. The laser frequency of the 1064 nm seed laser for the burst-mode laser was scanned during the burst to cover two neighboring absorption line pairs near 226 nm. The peak PLIF signal intensity varies along the axial (z) direction of the underexpanded jet as the laser frequency is scanned, which we attribute to the collisional shift induced by the flow and only revealed due to the narrow linewidth of the laser. A pseudo-Voight fit is applied to the LIF excitation spectra on a pixel-by-pixel basis to measure the spectral position of the peak intensity for the two transition pairs and their amplitude. The spectral position of the peak intensity is used to derive a frequency shift, which is separated into its collisional and Doppler components using the axisymmetric nature of the flow field. The amplitude of the measured peaks is used for two-line rotational thermometry. Challenges for quantitative measurements using such an approach are discussed, including measuring the spatial variations in the energy distribution of the laser sheet at a 100 kHz repetition rate and uncertainty/variability in the step size during the fast frequency scan.

laser induced fluorescence↗

Time-resolved populations of N 2 (A 3 Σ u + ,v) in nanosecond pulse discharge plasmas

Absolute time-resolved populations of N 2 in the excited A 3 Σ u + electronic state that are generated in a repetitive ns pulse discharge in nitrogen have been measured by Cavity Ring Down Spectroscopy (CRDS) and Tunable Diode Laser Spectroscopy (TDLAS). CRDS measurements of N 2 (A 3 Σ u + ,v = 0–2) populations are made in the discharge afterglow at pressures of 22 and 39 Torr. The data reduction procedure takes into account the linewidth of the pulsed laser source, which is comparable with the absorption linewidth and results in a non-single exponential ring down decay. Peak N 2 (A 3 Σ u + ,v = 0–2) populations after a 10-pulse ns discharge burst are in the range of 10 12 –10 13 cm -3 . In the afterglow, these populations exhibit a relatively slow decay with the characteristic time of approximately 500 μs, most likely due to the quenching by N atoms. TDLAS data have been taken at a higher pressure of 132 Torr. Absolute time-resolved N 2 (A 3 Σ u + ,v = 0,1) number densities are measured during ns pulse discharge bursts up to 5 pulses long and in the afterglow, peaking at 6·10 12 cm -3 and 3·1013 cm -3 , respectively. The results indicate that N 2 (A 3 Σ u + ) is generated after every discharge pulse on a 20–50 μs time scale, much longer compared to the discharge pulse duration of ~100 ns, and subsequently decays between the pulses. The decay rate increases during the discharge burst. In the afterglow, N 2 (A 3 Σ u + ,v = 0,1) population decay significantly more rapidly compared to the low-pressure CRDS conditions, with the characteristic time of approximately 160 μs after a 5-pulse discharge burst.

74 ATOMIC AND MOLECULAR PHYSICS↗

Plutonium Co-precipitation with Calcite

The mobility of plutonium (Pu) in the environment is affected by Pu–mineral interactions, such as adsorption–desorption and structural incorporation. Calcite (CaCO 3 ) is a common secondary phase in near surface environments and a major component of many rocks and soils and is expected to form as an alteration product of cement-based materials planned for use in geological repositories. The reactivity of the calcite surface and its ability to tolerate significant variations in its chemical composition through substitution of Ca for other cations make calcite a potentially important sink for environmental contaminants. Here, single crystals of calcite were synthesized from aqueous solutions in equilibrium with air containing Pu as either Pu(VI) or Pu(IV) and characterized using a combination of laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and X-ray absorption spectroscopy (XAS). These data are used to assess the amount, structure, and oxidation state of Pu co-precipitated into calcite, providing insight into the potential for Pu sequestration in calcite precipitates. Overall, the XAS and LA–ICP–MS data support the co-precipitation of plutonyl [Pu(VI/V)] in the bulk calcite, although the exact nature of the co-precipitated Pu complex is difficult to elucidate in the synthesized material. Co-precipitated plutonyl could be incorporated in either distorted Ca lattice sites or defect sites, and we provide evidence to suggest that Pu(VI) is reduced mainly to Pu(V) in the precipitated solid. LA–ICP–MS additionally shows that the co-precipitation of Pu(VI/V) is favored over the co-precipitation of Pu(IV). Altogether, our results suggest that Pu sequestration in calcite under environmental conditions could immobilize Pu and isolate it from groundwater interactions in contaminated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Leveraging the redox activities of cerium and dibenzotetrathiafulvalene to discover a photo-responsive magnetic material

Stimuli-responsive changes in lanthanide-based materials are a promising research direction. In this study, [DBTTF] 4 [Ce 2 Cl 10 ] DBTTF = dibenzotetrathiafulvalene (1) was synthesized by a light-induced crystallization, where photo-oxidation of DBTTF enables formation of the cerium dimer [Ce 2 Cl 10 ] 4− . Intermolecular interactions between the stacked organic units of the crystal result in charge transfer bands in the visible-NIR (near-infrared) region, evident in the solid-state absorption spectrum upon comparison with the solution spectrum. The assignments of the sublattice oxidation states were made with single-crystal X-ray diffraction (SC-XRD) structural characterization, Raman spectroscopy, X-ray absorption spectroscopy, and magnetometry. Continuous 532 nm laser irradiation of the microcrystalline solid modulates the redox states in 1, leading to ∼40% reduction in the observed magnetization at 2 K. Density functional theory PBE+U/HSE06 band structure calculations predict Mott insulating behavior in 1, with a bandgap of 0.54/0.81 eV, and further support the conjecture that the observed photo-induced change in magnetization results from electron transfer from the [Ce 2 Cl 10 ] 4− anions to the π-stacked [DBTTF] 2 2+ organic dimer subunits. An enhancement in conductivity is similarly observed upon 532 nm irradiation, determined by single-crystal transport measurements. The findings reveal that photo-responsive lanthanide-based materials can be achieved by integration of redox-active organic moieties with redox-active lanthanide cations for the realization of switchable, photo-magnetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pathways to excitation of atoms with bicircular laser pulses

We study the excitation of the hydrogen atom by bichromatic circularly polarized laser pulses using numerical solutions of the time-dependent Schrödinger equation. The results are in agreement with the selection rules for multiphoton processes in such fields, namely, excited states are populated in which orbital angular momentum and magnetic quantum numbers are either both odd or both even, independent of the relative helicity, peak intensity, and pulse duration of the pulses. For co-rotating pulses the results show that excitation predominantly proceeds to states with magnetic quantum number of the same helicity as the laser pulses. Besides pathways via direct photon absorption from the ground state our results indicate that a transfer of population among the Rydberg states occurs via Λ-type transitions. In the case of counter-rotating pulses the largest excitation probability is found for Rydberg states that differ in magnetic quantum number by Δm=±3. This pattern allows us to estimate how many photons from each of the two bichromatic fields have been absorbed. Finally, we confirm that a population in Rydberg states beyond a maximum orbital angular quantum number is unlikely.

74 ATOMIC AND MOLECULAR PHYSICS↗

High-precision monitoring of outgassing species in model extreme ultraviolet photoresists with a cavity ring-down spectrometer

Background Extreme ultraviolet (EUV) photoresists play a pivotal role in advancing nanopatterning technologies by balancing image quality and sensitivity. The outgassing behavior of photoresist thin films under EUV and deep ultraviolet (DUV) exposure reveals chemical details relevant to their performance. Aim Here, we focus on utilizing an analytical technique not previously used in photolithography, the tabletop cavity ring-down spectrometer, to investigate outgassing dynamics in EUV photoresists, enabling precise chemical identification and deeper insights into resist processing. Approach The spectrometer’s enhanced laser path length (∼ 20 km) and broadband absorption capabilities in the C–H overtone region allow for sensitive and temporally resolved detection of mixtures of outgassed species. Using a model resist comprising a polymer matrix with a photoacid generator and quencher, we analyzed the influence of time delays between exposure and post-exposure bake (PEB) as well as storage under varying environmental conditions. Results Suppression of isobutylene outgassing and thickness loss was observed with extended delays between exposure and PEB, potentially linked to water absorption and acid deactivation. The technique proved highly effective in distinguishing subtle chemical differences between processing stages. Conclusions Delay times and their environmental conditions, particularly humidity, reduce outgassing and thickness loss of photoresists during PEB, suggesting decreased acid-driven deprotection. This can potentially impact sensitivity, defectivity, and roughness of resist patterns, necessitating precise monitoring and control.

Extreme ultraviolet photoresists↗

High precision monitoring of outgassing species in model EUV photoresists with a cavity ring-down spectrometer

Extreme ultraviolet (EUV) photoresists play a pivotal role in advancing nanopatterning technologies by balancing image quality and sensitivity. The outgassing behavior of photoresist thin films under EUV and deep ultraviolet (DUV) exposure reveals chemical details relevant to their performance. This study focuses on utilizing an analytical technique not previously used in photolithography, the tabletop cavity ring-down spectrometer, to investigate outgassing dynamics in EUV photoresists, enabling precise chemical identification and deeper insights into resist processing. The spectrometer’s enhanced laser path length (~20 km) and broadband absorption capabilities in the CH overtone region allow for sensitive and temporally resolved detection of outgassed species. Using a model resist comprising a polymer matrix with a photoacid generator and quencher, we analyzed the influence of time delays between exposure and Post-Exposure Bake (PEB) as well as storage under varying environmental conditions. Suppression of isobutylene outgassing and thickness loss was observed with extended delays between exposure and PEB, potentially linked to water absorption and acid deactivation. The technique proved highly effective in distinguishing subtle chemical differences between processing stages. Delay times and their environmental conditions, particularly humidity, reduce outgassing and thickness loss of photoresists during PEB, suggesting decreased acid-driven deprotection. This can potentially impact sensitivity, defectivity, and roughness of resist patterns, necessitating precise monitoring and control.

Lüttgenau, Bernhard↗

Engineering a laser remote sensor for atmospheric pressure and temperature

A system for the remote sensing of atmospheric pressure and temperature is described. Resonant lines in the 7600 Angstrom oxygen A band region are used and an organic dye laser beam is tuned to measure line absorption changes with temperature or pressure. A reference beam outside this band is also transmitted for calibration. Using lidar techniques, profiling of these parameters with altitude can be accomplished.

Kalshoven, J. E., Jr.↗

Semiclassical theory of unimolecular dissociation induced by a laser field

A semiclassical nonperturbative theory of direct photodissociation in a laser field is developed in which photon absorption and dissociation are treated in a unified fashion. This is achieved by visualizing nuclear dynamics as a representative particle moving on electronic-field surfaces. Methods are described for calculating dissociation rates and probabilities by Monte Carlo selection of initial conditions and integration of classical trajectories on these surfaces. This unified theory reduces to the golden rule expression in the weak-field and short-time limits, and predicts nonlinear behavior, i.e., breakdown of the golden rule expression in intense fields. Field strengths above which lowest-order perturbation theory fails to work have been estimated for some systems. Useful physical insights provided by the electronic-field representation have been illustrated. Intense field effects are discussed which are amenable to experimental observation. The semiclassical methods used here are also applicable to multiple-surface dynamics in fieldfree unimolecular and bimolecular reactions.

Yuan, J.-M.↗

Laser spectroscopic detection of air pollutants

A brief review is presented of the operating principles and applications of laser systems for monitoring pollution based on absorption spectroscopy. Particular consideration is given to an active bistatic system involving a cooperative reflector; an active monostatic system involving natural reflectors; an active monostatic system involving aerosol backscattering; and passive monostatic heterodyne detection.

Hinkley, E. D.↗