Laboratory, ground-based, and airborne tunable diode laser systems: performance characteristics and applications in atmospheric studies

2 O) used as the target gas. One method utilizes the Allan variance. When our present aircraft system is operated in the laboratory, the Allan variance indicates a CH₂O detection limit of 0.031 ppbv for integration times of 25 s. This sensitivity corresponds to a minimum detectable absorbance of 1.0×10^-6, and this is within a factor of two of that reported by Werle et al. who used high-frequency modulation spectroscopy. The present instrument utilizes conventional low-frequency (2f=100 kHz) wavelength modulation. Instrument performance, obtained from replicate measurements of CH₂O standards acquired over time periods as long as 1.5 hours, on average resulted in a factor of two poorer precision than indicated by the Allan variance. Since replicate measurements precisely simulate the acquisition procedures employed, including the acquisition of sample and background spectra, they present a more meaningful measure of instrument performance. Preliminary evidence suggests that slow drifts in the laser wavelength control during acquisition of replicate measurements may play an important role in the above disparity. The resultant laser wavelength correction voltage, which is applied to counter such drifts, may also be a factor in this disparity. A limited number of replicate measurements with minimal drift in the laser wavelength yield much closer agreement between replicate and Allan variance precisions. Received: 19 March 1998/Revised version: 2 June 1998     

Pulsed quantum cascade laser instrument with compact design for rapid, high sensitivity measurements of trace gases in air

We have developed a compact instrument for sensitive, rapid and continuous measurement of trace gases in air, with results presented here for methane (CH₄), nitric oxide (NO), nitrous oxide (N₂O) and ammonia (NH₃). This instrument takes advantage of recent technology in quantum cascade (QC) lasers and infrared detectors, which allows high sensitivity without cryogenic liquids, e.g., 0.2 ppb (0.2×10^-9) of NH₃ in air in 1 s. One may substitute a QC laser operating at a different wavelength to measure other gases. The instrument operates continuously, requiring little operator attention, and web-based remote access is provided for instrument control, calibration and data retrieval. The instrument design includes a thermoelectrically (TE) cooled pulsed distributed feedback (DFB) QC laser, a low volume (0.5 l) multipass cell offering 76 m absorption path length and a TE cooled detector. Integrated software for laser control and data analysis using direct absorption provides quantitative trace gas measurements without calibration gases. The instrument may be applied to field measurements of gases of environmental concern. PACS  07.57.Ty; 42.62.Fi; 92.70.Cp     

A trace methane gas sensor using mid-infrared quantum cascaded laser at 7.5 μm

Presented is a compact instrument developed for in situ high-stable and sensitive continuous measurement of trace gases in air, with results shown for ambient methane (CH₄) concentration. This instrument takes advantage of recent technology in thermoelectrically cooled pulsed Fabry–Perot (FP) quantum cascaded (QC) laser driving in a pulse mode operating at 7.5 μm to monitor a well-isolated spectral line near the ν4 fundamental band of CH₄. A high-quality liquid nitrogen cooled mercury cadmium telluride mid-infrared detector with time discriminating electronics is used along with a total reflection coated gold ellipsoid mirror offering 20 cm single pass optical absorption in an open-path cell to achieve stability of 5.2 × 10^?3 under experimental condition of 200 ppm measured ambient CH₄. The instrument operates continuously, and integrated software for laser control using direct absorption provides quantitative trace gas measurements without calibration. One may substitute a QC laser operating at a different wavelength to measure other gases. The instrument can be applied to field measurements of gases of environmental concern.     

Single-mode optical pumping and superradiant emission in D2O and CH3F

Superradiant FIR emission in both D₂O and CH₃F has been investigated using a tunable single-mode CO₂ TEA laser as optical pump, and results compared with multimode pumping. The frequency offset of the absorbing transitions has been measured and compared to other work. Estimates of the dipole transition moments were also obtained from saturation broadening data. Fine structure of the CH₃F (Q12, K) lines have been resolved and compared with theory. High quantum conversion efficiencies were observed for several lines in D₂O: 38% (99 μm), 20% (385 μm) and 12.5% (121 μm) and in CH₃F 21% (496 μm).     

Applications of quantum cascade lasers for sensitive trace gas measurements of CO, CH4, N2O and HCHO

We describe here a sensitive quantum cascade laser absorption spectrometer (QCLAS) employed for aircraft based measurements during the GABRIEL 2005 and HOOVER 2006 and 2007 campaigns. This 3-channel instrument measures CO, HCHO, CH₄ and N₂O using a 64-m path double corner cube White cell. Performance of the instrument was examined for the four species and precisions for CO, N₂O and CH₄ were measured in the field to be 0.5, 0.5 and 0.7% respectively (2σ). The 1σ detection limit for HCHO was ∼500 pptv for a 2 s average, while signal averaging of the HCHO over a 2 min time interval resulted in a 150 pptv detection limit with a duty cycle of 60%. PACS  82.80.Gk; 07.88.+y; 42.62.-b; 92.60.H-     

First realization of new ps-10 mm-CO2-OFID laser systems with far-infrared laser gases as spectral filters

We demonstrate the first operation of a new ps 10 mm CO₂ laser system based on optical free induction decay (OFID) in far-infrared (FIR) laser gases, i.e. CH₃F, D₂O and NH₃. New phenomena are discussed.     

Adsorption of water and methanol on GaAs(110) surfaces studied by ultraviolet photoemission

UV photoemission spectroscopy (UPS) with He 1 radiation (hν = 21.2 eV) has been used to study the interaction of H₂O and CH₃OH with GaAs(110) surfaces prepared by cleavage in ultrahigh vacuum (UHV). For H₂O two molecularly adsorbed phases can be distinguished at 300 K: at low coverage H₂O is chemisorbed by its oxygen lone-pair orbital to the surface whereas for higher exposures a less perturbed species which resembles more a “physisorbed” or condensed H₂O layer is found. At 180 K only the less perturbed species can be identified. Also CH₃OH is chemisorbed molecularly at lower coverage with its oxygen end to the GaAs surface. For higher exposures two additional emission bands are observed which are interpreted as due to the methoxy radical CH₃O resulting from a partial decomposition of CH₃OH.     

Collision-induced rovibrational energy transfer in small polyatomic molecules: the role of intramolecular perturbations

ABSTRACT

Various forms of time-resolved optical double-resonance spectroscopy facilitate rotationally resolved measurements of collision-induced intramolecular vibration-to-vibration (V–V) energy-transfer processes, which take a gas-phase polyatomic molecule from one distinct rovibrational energy level to another. Of longstanding mechanistic interest are questions concerning the extent to which such V–V energy transfer (ET) may be influenced by intramolecular perturbations – notably Fermi resonance (and other anharmonic mixing effects) and Coriolis coupling – within polyatomic molecular rovibrational manifolds of interest. It is evident that quantum-mechanical interference effects can arise, either inhibiting or enhancing the probability of collision-induced ET in perturbed rovibrational manifolds of certain small gas-phase polyatomic molecules, notably CO₂, D₂CO and C₂H₂. This article focuses on a blend of high-resolution rovibrational spectroscopy (characterising initial and final molecular levels and their intramolecular perturbations) and collision dynamics (with colliding molecules defined in terms of isolated-molecule spectroscopic basis states). It aims to offer fresh insights and to consider some apparent mechanistic anomalies (e.g. collision-induced quasi-continuous background effects in the 4ν_CH rovibrational manifold of C₂H₂). Various reported experiments and related theoretical treatments are critically re-examined, in order to pose and address mechanistic questions some of which still challenge detailed understanding.     

Spectroscopy of CH<Subscript>4</Subscript> with a difference-frequency generation laser at 3.3 micron for atmospheric applications

The 3.25 micron spectral region is very suitable for the in situ sensing of CH₄ in the troposphere and the lower stratosphere with light-weight laser sensors. Several transitions of the strong fundamental ν ₃ band of CH₄ are revisited in this spectral region using an ultra-compact Difference-Frequency Generation (DFG) laser. Accurate intensities as well as self-broadening coefficients are reported for several manifolds that are particularly relevant to the monitoring of CH₄. The study is extended to over hundred transitions reachable over the tunability range of the laser. Moreover, this DFG laser is the light source of a new, highly-compact CH₄ laser spectrometer to be operated from weather balloon. The CH₄ laser sensor is described and preliminary flight results are reported.     

High sensitivity Faraday rotation spectrometer for hydroxyl radical detection at 2.8 μm

A distributed feedback diode laser based Faraday rotation spectroscopy (FRS) instrument was developed for detection of hydroxyl free radical (OH) at 2.8???m. Fast wavelength sweeping method was implemented and the instrument performances were compared with point-by-point wavelength tuning method. The fast sweeping operation mode showed the same short-term minimum detection limit and improved immunity to baseline drift. The effects of strong diamagnetic H₂O vapor absorption on FRS detection of paramagnetic OH were investigated. We demonstrated that in the case of strong H₂O vapor absorption, the magnitude of the FRS signal for OH might be affected due to changes in the received optical power. The effects of higher laser intensity on the FRS detection sensitivity were also studied experimentally.     

A comprehensive study of (CH3)2CHOC(S)SC(O)OCH3 using matrix isolation technique,X‐ray analysis,spectroscopic studies and theoretical calculations

Potassium isopropyl xanthate, (CH₃)₂CHOC(S)SK, reacts with methyl chloroformiate ClC(O)OCH₃ to yield (methoxycarbonyl) (2‐propoxythiocarbonyl) sulfide, (CH₃)₂CHOC(S)SC(O)OCH₃. This novel xanthogen formate was characterized by ¹H and ¹³C{¹H} NMR spectroscopy, mass spectrometry and IR and Raman spectroscopy. The structure of a single crystal of (CH₃)₂CHOC(S)SC(O)OCH₃ was determined by X‐ray diffraction analysis at 173 K. The conformational properties have been studied by liquid IR and Raman spectroscopy, matrix isolation spectroscopy together with photochemical studies and quantum chemical calculations (HF and B3LYP methods with the 6‐31+G* basis set). The analysis of the IR spectrum of liquid (CH₃)₂CHOC(S)SC(O)OCH₃ suggests the presence of two conformers in equilibrium at room temperature. However, in the photochemical matrix study, an equilibrium of three conformers was detected. These forms were further characterized by theoretical calculations. Different photolysis products, such as CH₃OC(O)SCH(CH₃)₂, OCS, CO, CO₂ and CS₂, were identified by matrix spectroscopy. The IR absorptions of CH₃OC(O)SCH(CH₃)₂, for which literature data are scarce, were analysed in the light of the results of appropriate theoretical calculations. Copyright © 2009 John Wiley & Sons, Ltd.     

Single-QCL-based absorption sensor for simultaneous trace-gas detection of CH4 and N2O

A quantum cascade laser (QCL)-based absorption sensor for the simultaneous dual-species monitoring of CH₄ and N₂O was developed using a novel compact multipass gas cell (MGC). This sensor uses a thermoelectrically cooled, continuous wave, distributed feedback QCL operating at ~7.8 µm. The QCL wavelength was scanned over two neighboring CH₄ (1275.04 cm^?1) and N₂O (1274.61 cm^?1) lines at a 1 Hz repetition rate. Wavelength modulation spectroscopy (f = 10 kHz) with second harmonic (2f) detection was performed to enhance the signal-to-noise ratio. An ultra-compact MGC (16.9 cm long and a 225 ml sampling volume) was utilized to achieve an effective optical path length of 57.6 m. With such a sensor configuration, a detection limit of 5.9 ppb for CH₄ and 2.6 ppb for N₂O was achieved, respectively, at 1-s averaging time.     

Nitromethane pyrolysis in shock tubes and a micro flow reactor with a controlled temperature profile

Nitromethane has many applications, such as in racing, as a gasoline fuel additive, and as a monopropellant. Despite a large number of studies and the small size of the molecule, the combustion chemistry of nitromethane is still not well understood. To improve models, the pyrolysis of nitromethane (CH₃NO₂) was investigated experimentally in shock tubes and in a micro flow reactor with a controlled temperature profile (MFR), under dilute conditions. Several spectroscopic diagnostics were used in the shock tubes to follow the concentration time histories of CO, H₂O (both using IR laser absorption), and CH₃NO₂ (UV light absorption). A quadrupole mass spectrometer was used to measure CH₃NO₂, NO₂, CH₄, C₂H₄, and C₂H₂ at various temperatures with the MFR. These unique experimental results were compared to modern, detailed kinetics models from the literature, and no mechanism was able to reproduce these data over the wide range of conditions investigated. Predictions for the CO and H₂O levels were generally inaccurate, and the CH₄, C₂H₄, and C₂H₂ predictions were poor in most cases for the MFR data. Importantly, all models largely differ in their predictions. A numerical analysis was performed to identify ways to improve the next generation of nitromethane models. Results indicate that nitromethane decomposition needs to be improved below 1050 K, and that hydrocarbon-NOx interactions still need to be further investigated.     

Far infrared laser lines produced by methanol and its isotopic species: A review

Methanol (CH₃OH) is considered today one of the most important active media for the generation of laser radiation in the far-infrared (FIR) spectral region. Together with ten of its other isotopic species, it is responsible for the major part of the laser lines generated by the optical pumping technique. Due to the extreme importance of those molecules as laser generators, we understood that there was a necessity of a comprehensive work which would include as much pratical information as possible about each line.Chang et al⁽¹⁾ early recognized methanol as a source of strong FIR laser lines. Since then, more than 100 papers were published containing information about new laser emission. Recently, Moruzzi et al⁽¹¹⁴⁾ presented a review of 575 lines produced by¹²CH₃OH. In the present paper, we have extended the review to the various isotopic modifications of this molecule (namely¹³CH₃OH, CD₃OH,¹³CD₃OH, CD₃OD,¹³CD₃OD, CH₃OD, CH ₃ ¹⁸ OH, CH₂DOH, CH₂DOD and CHD₂OH), a total of nearly 2000 lines with wavelengths ranging from 19µm to 3030µm.     

Enrichment of carbon-14 by selective laser photolysis of formaldehyde

Using a frequency-doubled dye laser, simultaneous high-resolution spectra of¹⁴CH₂O and¹²CH₂O between 290 and 345 nm were measured. About 30 lines with spectral selectivities for¹⁴C≳50 were found. Photolyses on one such line at 326.94 nm of a dilute mixture of¹⁴CH₂O in natural CH₂O gave one-step enrichment factors of up to 150, with μg yields of enriched product. Since a factor of 150 in¹⁴C concentration corresponds to ∼7.2 half lives or 41,000 years, laser enrichment of archaeological samples, especially when combined with direct detection methods of¹⁴C abundance measurement, can greatly improve the range of radiocarbon dating.     

Space-borne remote sensing of CO2, CH4, and N2O by integrated path differential absorption lidar: a sensitivity analysis

CO₂, CH₄, and N₂O are recognised as the most important greenhouse gases, the concentrations of which increase rapidly through human activities. Space-borne integrated path differential absorption lidar allows global observations at day and night over land and water surfaces in all climates. In this study we investigate potential sources of measurement errors and compare them with the scientific requirements. Our simulations reveal that moderate-size instruments in terms of telescope aperture (0.5–1.5 m) and laser average power (0.4–4 W) potentially have a low random error of the greenhouse gas column which is 0.2% for CO₂ and 0.4% for CH₄ for soundings at 1.6 μm, 0.4% for CO₂ at 2.1 μm, 0.6% for CH₄ at 2.3 μm, and 0.3% for N₂O at 3.9 μm. Coherent detection instruments are generally limited by speckle noise, while direct detection instruments suffer from high detector noise using current technology. The wavelength selection in the vicinity of the absorption line is critical as it controls the height region of highest sensitivity, the temperature cross-sensitivity, and the demands on frequency stability. For CO₂, an error budget of 0.08% is derived from our analysis of the sources of systematic errors. Among them, the frequency stability of ± 0.3 MHz for the laser transmitter and spectral purity of 99.9% in conjunction with a narrow-band spectral filter of 1 GHz (FWHM) are identified to be challenging instrument requirements for a direct detection CO₂ system operating at 1.6 μm. PACS 42.68.Wt; 95.75.Qr     

碳、氮和氧族元素取代对2,1,3-苯并噻二唑衍生物的电子、光谱、电荷传输性质影响的理论研究

采用量子化学方法设计并研究了一系列CH₂、NH、O和Se取代的2,1,3-苯并噻二唑衍生物的电子性质、光谱性质和电荷传输性质．采用的研究方法是从头算Hartree-Fock和密度泛函方法．研究结果表明,中心芳环的S原子分别被CH₂、NH、O和Se取代后,母体分子的电子性质、光谱性质以及电荷传输性质得到了很好的调节．根据得到的理论研究结果,在2,1,3-苯并噻二唑衍生物基础上进行结构修饰得到的一系列分子可以作为有机发光二极管中的有机发光材料.     

Preliminary results of an aircraft system based on near-IR diode lasers for continuous measurements of the concentration of methane, carbon dioxide, water and its isotopes

The Federal Agency for Hydrometeorology of the Russian Federation created the flying laboratory on board the passenger airplane Yak-42D for geophysical monitoring of the environment, including aircraft measurements of vertical concentrations of greenhouse gases in the troposphere. Within the limits of this project, General Physics Institute of the Russian Academy of Science developed airborne tunable diode laser spectrometer (TDLS) on the basis of diode lasers of a near-IR range for measurement of the altitude profiles of CO₂, CH₄, H₂O and its isotopes. TDLS complex was integrated aboard in standard 19-in. rack. Air samples, taken over an aircraft on the pipeline, were injected into the optical cell. Using the system of inflow and heating, the air was set laminar with a flowrate of 0.2?l/s at a reduced pressure of 100?mbar for detecting narrow absorption lines of water vapor isotopes. For registration of the absorption spectra and for the measurement of greenhouse gas concentrations in online mode, modulation-correlation technique was used. Diode laser spectrometer output data were transferred to the airborne central computer. Sensitivity of TDLS measurements was 20?C30?ppm for water, 3?C4?ppm for CO₂ and 20?C25?ppb for CH₄. Time of one-unit measurement is about 30?ms.     

FIR Laser Lines from CH3OD: A Review

The methanol isotopic species CH₃OD has also proved to be an efficient and powerful medium to generate radiation in the far infrared (FIR) region. After the critical review of 1994, six papers have been published dealing with new FIR laser lines from this molecule. As a consequence of the use of wide tunability waveguide CO₂ lasers as well as a new pulsed CO₂ laser operating at hot and sequential bands, as of optical pumping sources, the total number of the FIR laser lines increased from 122 in 1994 to 227 today. In this communication we present an updated and complete catalogue of FIR laser lines generated from CH₃OD. Information on wavelength, offset, relative polarization, intensity, and optimum operation pressure is generally available.