Tunable Diode Laser (TDL) Development for Trace Gas Spectroscopy and Metrology Systems
The current status of tunable diode lasers (TDLs) for spectroscopy and metrology systems is reviewed.
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The current status of tunable diode lasers (TDLs) for spectroscopy and metrology systems is reviewed.
When a thin foil is inserted in the beam of a beam-gas experiment, the beam particle state populations are driven far from their beam-gas equilibrium values. Downstream from the foil, the 'new beam' and gas species interact to produce a new equilibrium, usually different from the beam-gas equilibrium. Experimental results are presented to demonstrate this effect and to show how relative cross-section measurements can be used to study the beam-foil interaction.
We report on the successful synthesis of diammonium magnesium dihydrogendiphosphate (V) dihydrate compound (NH 4 ) 2 Mg(H 2 P 2 O 7 ) 2 •2H 2 O using a wet chemical route. Single crystal X-ray diffraction analysis and micro Raman spectroscopy are employed to characterize the compound. We demonstrate, using a multidisciplinary approach, that this compound is ideal for carbon dioxide (CO 2 ) capture in addition to other anthropogenic gasses. We show here -from both an experimental as well as from a density functional theory (DFT) calculations routes- the potential for adopting this compound into domestic air-conditioning units (ACUs). From these experiments, the resistance to bacterial growth is also investigated, which is critical for the adoption of this compound in ACUs. Our compound exhibits a higher methane (CH 4 ) sorptivity as compared to CO 2 at 25 °C and 45 °C under pressures up to 50 bars. Furthermore, DFT electronic structure calculations are used to compute the main structural and electronic properties of the compound, taking into consideration the characteristics of the identified pores as a function of the progressive CO 2 vs. CH 4 loadings. Finally, the antibacterial assay reveals a strong antibacterial activity against the tested Gram-positive and Gram-negative bacteria, with a large zone of inhibition against the tested E. Coli, S. Aureus and K. Pneumonia
Recent advances in hybrid integrated silicon photonic (SiPh) technologies are enabling the migration of conventional free-space optical spectroscopic sensors onto a compact on-chip platform [1-3]. In addition to the small spatial footprint and power efficiency, we envision such sensors to be scalably manufactured using existing CMOS-compatible foundry processes, thus providing disruptive SWaP-C (size, weight, power, and cost) benefits in contrast to commercially available optical sensors. Initial demonstration of evanescent TDLAS (tunable diode laser absorption spectroscopy) of methane (CH4) on a passive SiPh waveguide has indicated minimum fractional absorption of (αL)min = 3.3×10-5 Hz-1/2, which is on-par with state-of-art open-path TDLAS sensor systems [4]. Given the general recent movement toward cleaner fuels, CH4 fugitive emissions monitoring is of significant interest given the extremely high radiative forcing potential [5]. For a nominal waveguide length of 30 cm with Γ = 25 % evanescent exposure, this corresponds to ~ 10 ppmv detection sensitivity at 1 s integration time, and further sensitivity enhancement is expected with even longer waveguides, as the laser RIN typically dominates our measurements at nominal waveguide lengths. Despite the excellent sensitivities for short-term integration periods, long-term measurements (> 10 s) are potentially limited on a silicon platform due to the high material thermo-optic coefficient, resulting in significant susceptibility of Fabry-Perot etalons to drift in the presence of even small (~ 1 mK) thermal fluctuations. To this end, customized spectral fitting algorithms have played a significant role in both fringe drift mitigation and peak detection fidelity (e.g. in the presence of a passing CH4 plume), which are crucial for enhancing long-term stability without the need for frequent sensor recalibration. A variety of spectral algorithms have been designed for this purpose, and details will be presented at the meeting.
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IR gas correlation spectroscopy is a sensitive technique for the measurement of small Doppler shifts in spectra. This technique also exhibits several important advantages over alternative methods in the remote sensing of stratospheric and mesospheric winds from spacecraft. Attention is presently given to laboratory tests demonstrating gas correlation spectroscopy's quantitative measurement of small Doppler shifts in spectra, whose close agreement with theoretical predictions suggests that measurements of the change in the radiant flux through a gas correlation spectrometer can be used to measure the relative velocity between gas and instrument for a moving parcel of gas.
Spectroscopy of fast atoms resulting from fast ion impact with gas targets and electron capture into excited state
Gas phase ion-molecule phosphine reactions in pure and binary mixtures by ion cyclotron resonance spectroscopy, considering acidity and basicity
Advanced reprocessing schemes such as the Zircex process are important for continued development of the nuclear fuel cycle. The hydrochlorination reaction of the Zircex process flow sheet for metallic fuels has a known off-gas stream of H 2 (g) and HCl. The flow sheet can be simplified through HCl recycling, which requires detection and quantification of any residual H 2 (g) for safety and purity. In this work, commercially available Raman spectroscopy was applied for low-level, on-line detection of H 2 (g) in process gas streams, and parameters were adjusted to optimize the H 2 (g) Raman signal. Increasing the number of scans and exposure time in the spectrometer increased the signal-to-noise ratio of the H 2 (g) Raman signal, while the gas flow rate was optimized at 2.3 L/min. The limit of detection for H 2 (g) was estimated to be 2,100 ppm H 2 (g) in an N 2 (g) background. This scoping study for the application of Raman spectroscopy for on-line measurements of H 2 (g) shows that H 2 (g) can be detected at low levels (approximately 5% of the lower explosive limit (LEL)) in flowing gas streams.
A new gas-correlation spectroscopy technique is described which uses electrooptic phase modulation (EOPM) of atmospheric emission spectra together with a reference cell to selectively detect radiatively active gases. Laboratory results demonstrate that the EOPM gas-correlation technique is a sensitive approach to species abundance measurements, and support the feasibility of an instrument for measurement of winds in the stratosphere and mesosphere using an EOPM. Through the measurement of wind-induced Doppler shifts in the spectra of atmospheric species, this instrument offers a means of monitoring the wind field in the 20-100 km altitude range from a satellite.
Absolute frequency measurement and spectroscopy of gas laser transitions in far IR, analyzing Zeeman effect
Optical- and IR-maser spectroscopy of inhomogeneously broadened resonances, using gas lasers
Electro-optic phase-modulation gas-correlation spectroscopy demonstrated in laboratory tests promising candidate technique for remote sensing of gases, temperatures, and wind velocities in atmosphere. In technique radiation emitted by sample atmosphere passed through electro-optic phase modulator, and modulated and unmodulated versions of spectrum alternately passed through reference absorption cell containing gas to be detected. Radiation emerging from reference cell band-pass filtered and detected. Correlation signal is difference in intensity between phase-modulated and unmodulated detected signals.
A widely tunable infrared spectrometer based on difference frequency generation (DFG) has been developed for organic trace gas detection by laser absorption spectroscopy. On-line measurements of concentration of various hydrocarbons, such as acetylene, benzene, and ethylene, were investigated using high-resolution DFG trace gas spectroscopy for highly sensitive detection.
Gas hydrates form at high pressure and low temperatures in marine sediments and permafrost regions of the earth. Despite forming in nanoporous structures, gas hydrates have been extensively studied only in bulk. Understanding nucleation and growth of gas hydrates in nonporous confinement can help create ways for storage and utilization as a future energy source. Herein, we introduce a new method for studying crystal orientation/tilt during tetrahydrofuran (THF) hydrate crystallization under the influence of nano-confinement using polarized Raman spectroscopy. Uniform cylindrical nanometer size pores of anodic aluminum oxide (AAO) are used as a model nano-confinement, and hydrate experiments are performed in a glass microsystem for control of the flash hydrate nucleation kinetics and analysis via in situ polarized Raman spectroscopy. The average THF hydrate crystal tilt of 56 ± 1° and 30.5 ± 0.5° were observed for the 20 nm and 40 nm diameter pores, respectively. Crystal tilt observed in 20 and 40-nanometer-size pores was proportional to the pore diameter, resulting in lower tilt relative to the axis of the confinement at larger diameter pores. Finally, the results indicate that the hydrates nucleation and growth mechanism can depend on the nanoconfinement size. A 1.6 ± 0.01 °C to 1.8 ± 0.01 °C depression in melting point compared to the bulk is predicted using the Gibbs–Thomson equation as a direct effect of nucleation in confinement on the hydrate properties.
Gas phase ion-molecule clusters of the form V + (H 2 O) n (n = 1-30) are produced by laser vaporization in a supersonic expansion. These ions are analyzed and mass-selected with a time-of-flight mass spectrometer and investigated with infrared laser photodissociation spectroscopy. The small clusters (n ≤ 7) are studied with argon tagging, while the larger clusters are studied via the elimination of water molecules. The vibrational spectra for the small clusters include only free O-H stretching vibrations, while larger clusters exhibit red-shifted hydrogen bonding vibrations. The spectral patterns reveal that the coordination around V + ions is completed with four water molecules. A symmetric square-planar structure forms for the n = 4 ion, and this becomes the core ion in larger structures. Clusters up to n = 8 have mostly two-dimensional structures, but hydrogen bonding networks evolve to three-dimensional structures in larger clusters. The free O-H vibration of AAD (acceptor-acceptor-donor) coordinated surface molecules converges to a frequency near that of bulk water by the cluster size of n = 30. However, the splitting of this vibration for AAD- versus AD-coordinated molecules is still different compared to other singly-charged or doubly-charged cation-water clusters. Finally, this indicates that cation identity and charge-site location in the cluster can produce discernible spectral differences for clusters in this size range.
A method directs a gas of interest into a minicell and uses an emitting laser to produce laser emission light that is directed into the minicell and onto the gas of interest. The laser emission light is reflected within the cell to make multipasses through the gas of interest. After the multipasses through the gas of interest the laser light is analyzed to produces gas spectroscopy data. The minicell receives the gas of interest and a transmitting optic connected to the minicell that directs a beam into the minicell and onto the gas of interest. A receiving optic connected to the minicell receives the beam from the gas of interest and directs the beam to an analyzer that produces gas spectroscopy data.
In this study, the close physical proximity of the Gas Puff Imaging (GPI) and Beam Emission Spectroscopy (BES) diagnostics on the National Spherical torus Experiment (NSTX) is leveraged to directly compare fluctuation measurements, and to study the local effects of the GPI neutral deuterium puff during H-mode plasmas without large Edge Localized Modes. The GPI and BES views on NSTX provide partially overlapping coverage of the edge and scrape-off layer (SOL) regions above the outboard midplane. The separation in the toroidal direction is 16°, and field lines passing through diagnostic views are separated by ∼20 cm in the direction perpendicular to the magnetic field. Strong cross-correlation is observed, and strong cross-coherence is seen for frequencies between 5 and 15 kHz. Also, probability distribution functions of fluctuations measured ∼3 cm inside the separatrix exhibit only minor deviations from a normal distribution for both diagnostics, and good agreement between correlation length estimates, decorrelation times, and structure velocities is found at the ±40% level. While the two instruments agree closely in many respects, some discrepancies are observed. Most notably, GPI normalized fluctuation levels exceed BES fluctuations by a factor of ∼9. BES mean intensity is found to be sensitive to the GPI neutral gas puff, and BES normalized fluctuation levels for frequencies between 1 and 10 kHz are observed to increase during the GPI puff.