Laser-based photoacoustic ammonia sensors for industrial applications

An industrial trace-ammonia sensor based on photoacoustic spectroscopy and CO₂ lasers has been developed for measuring ammonia with a 1σ detection limit of 220 parts-per-trillion (ppt) in an integration time of 30 s. The instrument response time for measuring ammonia was 200 s, limited by adsorption effects due to the polar nature of ammonia. The minimum detectable fractional absorbance was 2.0×10^-7, and the minimum normalized detectable absorption coefficient for this system was 2.4×10^-7 W cm^-1/z. The 9R(30) transition of the CO₂ laser at 9.22 μm with 2 W of output power was used to probe the strong sR(5,K) multiplet of ammonia at the same wavelength. This sensor was demonstrated with an optically multiplexed configuration for simultaneous measurement in four cells. Received: 3 April 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-310/458-0171, E-mail: webber@pranalytica.com     

Infrared laser stark shift spectroscopy in ammonia

The Stark effect in ammonia has been theoretically and experimentally analyzed using lead salt tunable diode laser absorption spectroscopy and CO₂ laser absorption spectroscopy of several absorption lines around 1050 cm^–1 applied to an all-optical sensor for measuring of electric field strength. Measurements of the Stark splitting effect of theaR(5,K) ammonia lines forK=1–5 as well as for the sR(3,K) lines forK=0–3 have been made at Doppler broadening pressures and for several different electric field strengths. Theoretical electric field dependent energy levels have been evaluated by diagonalization of a 6×6 energy matrix constructed using both electric field independent and dependent terms. From the theoretical analysis the resolution can be predicted and optimized both in the Doppler broadened and in the pressure broadened regimes. The predicted resolution is 0.5% at an electric field strength of 20 kV/cm. The theoretical calculations and the experimental data recorded with the tunable diode laser system were compared with independent measurements made with a CO₂ laser system. The agreement between experimentally recorded and theoretically calculated spectra is good which indicates that the theoretical model is satisfactory for our purposes. The contribution from the normally forbidden ssR(5, 3) ammonia line to the absorption at theP(12) CO₂ laser line in the 9 m band is briefly discussed.     

Multiwatt optically pumped ammonia laser operation in the 12–13 μm

Design and operating caracteristics of high pulse repetition rate NH₃ laser producing up to 20 W of average output power are described. The NH₃ laser, operating in the 12–13 μm region was optically pumped with a high pulse repetition rate TEA CO₂ laser. Dependences of the NH₃ laser output on the pump energy, ammonia and buffer gas pressures and pulse repetition rate have been studied. The conversion efficiency of up to 16% has been received.     

New CW FIR laser lines obtained in ammonia pumped by a CO2 laser, using the Stark tuning method

We report fifty seven CW FIR emissions observed in NH₃, by resonant pumping with a CO₂ laser. Exact coincidences between IR absorption lines of the gas and emission lines of the CO₂ laser have been carried out by Stark tuning. IR frequency shifts, up to 30 GHz, have allowed the pumping of forty three NH₃ transitions.These FIR emissions correspond to thirty one different wavelengths in the 50–400 m range; eighteen ones of them are new emitted wavelengths by pumping with the CO₂ laser.     

Infrared multiple photon decomposition of CHBrF2 induced by a free-electron laser

2 . The laser generates an intense infrared macropulse with a duration of 17 μs; the macropulse consists of a train of 380 micropulses, each of which has a duration of a few picoseconds. The fluence of a macropulse was estimated to be about 16 Jcm^-2 at a beam waist. Peak wavelengths were set in the range of 9–10 μm. The macropulse induced the IRMPD of 1 and 5 Torr CHBrF₂; most of molecules in the focal region seemed to decompose at a wavelength of 9.3 μm. The mechanism is the initial decomposition of CHBrF₂ to CF₂ and HBr, followed by the dimerization of CF₂ to form C₂F₄. The decomposition was found to be isotopically selective at 9.7 μm; the final product C₂F₄ had a ¹³C atomic fraction of 6%. Th e addition of CO₂ to CHBrF₂ significantly decreased the yield of C₂F₄. vibrationally excited CHBrF₂ molecules produced by laser pulses were efficiently deactivated by CO₂ molecules. Received: 7 October 1996     

Frequency-stabilized cavity ring-down spectroscopy measurements of carbon dioxide isotopic ratios

Carbon dioxide (CO₂) isotopic ratios on samples of pure CO₂ were measured in the 1.6 μm wavelength region using the frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) technique. We present CO₂ absorption spectra with peak signal-to-noise ratios as high as 28,000:1. Measured single-spectrum signal-to-noise ratios were as high as 8900:1, 10,000:1, and 1700:1 for ¹³C/¹²C, ¹⁸O/¹⁶O, and ¹⁷O/¹⁶O, respectively. In addition, we demonstrate the importance of utilizing the Galatry line profile in the spectrum analysis. The use of the Voigt line profile, which neglects the observed collisional narrowing, leads to large systematic errors which are transition-dependent and vary with temperature and pressure. While the relatively low intensities of CO₂ transitions near λ=1.6 μm make this spectral region non-optimal, the sensitivity and stability of FS-CRDS enabled measurement precision of pure CO₂ samples which are comparable to those of other optical techniques which operate at far more propitious wavelengths. These results indicate that a FS-CRDS spectrometer designed to probe CO₂ bands near wavelengths of 2.0 μm or 4.3 μm could achieve significantly improved precision over the present instrument and likely be competitive with mass spectrometric methods.     

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     

Discovery and frequency measurement of far-infrared laser emissions generated by optically pumped CH2DOH

A recently improved three-laser heterodyne system was used to frequency measure ten previously observed optically pumped far-infrared (FIR) laser emissions from the partially deuterated methanol isotopologue CH₂DOH. Also, a 64.0 μm FIR emission generated by the 9P32 line of the carbon dioxide (CO₂) laser was discovered and frequency measured. These newly measured frequencies have fractional uncertainties on the order of ±2×10^-7 and correspond to laser wavelengths ranging from 42.6 to 152.7 μm. The offset frequency for the CO₂ pump laser was measured for twenty-two CH₂DOH FIR laser emissions. PACS 07.57.Hm; 42.55Lt; 42.62.Eh     

Stimulated rotational Raman scattering at multiwavelength under tea CO2 laser pumping with a multiple-pass cell

Stimulated rotational Raman scattering (SRRS) at multiwavelength pumped by TEA CO₂ laser was demonstrated in this paper. Raman mediums were cooled by liquid-N₂ and a multiple-pass cell (MPC) with 25 passes was designed and used. When the para-H2 was pumped by single-longitudinal-mode (SLM) circular polarized TEA CO₂ laser on 10P(20), 9P(20), and 10R(20), 50 mJ 16.95 μm, 350 mJ 14.44 μm, and 536 mJ 16.9 μm radiations were obtained, corresponding to energy conversion efficiency of 1.2, 11.7, and 13.4%, respectively. When the ortho-D₂ was pumped by CO₂ laser on 10R(18), 108 mJ 12.57 μm Raman laser was obtained with energy conversion efficiency of 2.9%.     

New short-wavelength laser emissions from partially deuterated methanol isotopes

The partially deuterated isotopes of methanol, CH₂DOH and CHD₂OH, have been reinvestigated as sources of far-infrared (FIR) laser emissions using an optically pumped molecular laser (OPML) system recently designed for wavelengths below 150 μm. With this system, 10 new FIR laser emissions from these isotopes ranging from 32.8 to 174.6 μm have been discovered. This includes the shortest known OPML emission from CHD₂OH, at 32.8 μm. These lines are reported with their operating pressure, polarizations relative to the CO₂ pump laser and wavelengths, measured to ±0.5 μm. In addition, polarizations for three previously observed FIR laser lines from CHD₂OH were measured for the first time. This paper is dedicated to the memory of Dr. K.M. Evenson, a pioneer in the field for his role in the development of optically pumped molecular lasers and their use in laser frequency measurements and the laser magnetic resonance technique. His scientific expertise, guidance, mentoring and friendship will be greatly missed. Received: 27 March 2002 / Published online: 8 May 2002     

Measurements of high-pressure CO2 absorption near 2.0 μm and implications on tunable diode laser sensor design

A tunable diode laser (TDL) is used to measure the absorption spectra of the R46 through R54 transitions of the 20012←00001 band of CO₂ near 2.0 μm (5000 cm⁻¹) at room temperature and pressures to 10 atm (densities to 9.2 amagat). Spectra are recorded using direct absorption spectroscopy and wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) in a mixture containing 11% CO₂ in air. The direct absorption spectra are influenced by non-Lorentzian effects including finite-duration collisions which perturb far-wing absorption, and an empirical χ-function correction to the Voigt line shape is shown to greatly reduce error in the spectral model. WMS-2f spectra are shown to be at least a factor of four less-influenced by non-Lorentzian effects in this region, making this approach more resistant to errors in the far-wing line shape model and allowing a comparison between the spectral parameters of HITRAN and a new database which includes pressure-induced shift coefficients. The implications of these measurements on practical, high-pressure CO₂ sensor design are discussed.     

Hard tissue ablation with a free running Er:YAG and a Q-switched CO2 laser: a comparative study

The Er:YAG and the CO₂ laser are competitors in the field of hard tissue ablation. The use of Er:YAG lasers (2.94 μm, pulse length _L of 100 to 200 μs) show smaller areas of thermal defects then ‘‘superpulsed’’ CO₂ lasers with pulse lengths of approximately 100 μs. Only the development of a Q-switched CO₂ laser (9.6 μm, τ_L=250 ns) allowed for similar results. In this paper new results for the Er:YAG and the Q-switched CO₂ laser under the influence of water spray will be presented. Several parameters are of special interest for these investigations: the specific ablation energy, which shows a minimum for the CO₂ laser at an energy density of 9 J/cm ² and a broad shallow minimum in the range of 10 to 70 J/cm² for the Er:YAG laser, and comparison of the cut-shape and depth. Surface effects and cutting velocity are discussed based on SEM pictures. Received: 19 July 2000 / Revised version: 1 November 2000 / Published online: 30 November 2000     

Diode laser spectroscopy of H2O and CO2 in the 1.877-μm region for the in situ monitoring of the Martian atmosphere

A diode laser spectrometer was used in the laboratory to study H₂O and CO₂ line intensities and self-broadening coefficients around 1.877 μm. The spectral region ranging from 5327 cm^-1 to 5329 cm^-1, which is suitable for the in situ sensing of water vapor and carbon dioxide in the Martian atmosphere, was studied using a distributed feedback GaInSb diode laser from Nanoplus GmbH. We have studied one line from the (011)←(000)band of H₂O and two lines from the (01¹2)_I←(000) band of CO₂. The results of intensity and self-broadening measurements are compared to available databases, ab initio calculations and previous experimental determinations. Finally, we discuss the current development of the tunable diode laser absorption spectrometer instrument, a laser diode sensor devoted to the in situ measurement of H₂O and CO₂ in the Martian atmosphere. PACS 07.57.Ty; 07.87.+v     

Investigation of 13CH3OH methanol: new laser lines and assignments

We have reinvestigated ¹³CH₃OH as a source of far-infrared (FIR) laser emission using a CO₂ laser as a pumping source. Thirty new FIR laser lines in the range 36.5 μm to 202.6 μm were observed and characterized. Five of them have wavelengths between 36.5 and 75 μm and have sufficient intensity to be used in LMR spectroscopy. Using Fourier-transform spectroscopic data in the infrared (IR) and FIR regions we have determined the assignment for 10 FIR laser transitions and predict nine frequencies for laser lines which have yet to be observed. Received: 17 July 2000 / Published online: 6 December 2000     

Measurement of the transition strength of the 00o2 9.4 μm sequence band in CO2 using a tunable diode laser

We report the first accurate measurements of the transition strengths and linewidths of the 00^o2 9.4 μm sequence lines of CO₂. This sequence band is found to be very similar to the regular 00^o1 laser band, except for an experimentally determined factor of 1.89±0.12 increase in transition strength (if the CO₂ molecule is treated as a simple harmonic oscillator the theoretical increase in transition strength is 2.0). The laser absorption spectrometer used for these measurements can detect absorption coefficients in CO₂ of ≈10⁻⁷ m⁻¹, and we discuss the feasibility of using this sensitivity to monitor rare isotopic forms of CO₂. Work supported by the Department of National Health and Welfare, Environment Canada, Ontario Ministry of the Environment, and Atmospheric Environment Service, Environment Canada.     

Infrared laser emission in two-photon pumped sodium vapour

We report infrared laser emission in the region of 3 to 5 μm from sodium vapour optically pumped by a pulsed dye laser with wavelengths ranging from 585 to 610nm. Twophoton excitation processes are believed to be responsible for the primary excitation. Both molecular transitions (4 to 5 μm) between high lying states, and atomic transitions (5² S _1/2−4² P _3/2,1/2 at 3.41 μm) have been identified.     

Optoacoustic laser spectroscopy of excited vibrational molecular states

A new detection method for absorption from excited vibrational states is suggested, based on optoacoustic detection of weak absorption in a heated gas. Using this method CO₂ laser radiation (λ=9.6 μm) absorption was investigated from excited vibrational states of CO₂, BCl₃, and BF₃ molecules.     

Open-path trace gas detection of ammonia based on cavity-enhanced absorption spectroscopy

A compact open-path optical ammonia detector is developed. A tunable external-cavity diode laser operating at 1.5 μm is used to probe absorptions of ammonia via the cavity-enhanced absorption (CEA) technique. The detector is tested in a climate chamber. The sensitivity and linearity of this system are studied for ammonia and water at atmospheric pressure. A cluster of closely spaced rovibrational overtone and combination band transitions, observed as one broad absorption feature, is used for the detection of ammonia. On these molecular transitions a detection limit of 100 ppb (1 s) is determined. The ammonia measurements are calibrated independently with a chemiluminescence monitor. Compared to other optical open-path detection methods in the 1–2 μm region, the present result shows an improved sensitivity for contactless ammonia detection by over one order of magnitude. Using the same set-up, a detection limit of 100 ppm (1 s) is determined for the detection of water at atmospheric pressure. Received: 19 January 2000 / Revised version: 6 March 2000 / Published online: 7 June 2000     

$90^{\circ}$ phase-matched parametric frequency conversion in AgGa1-xInxS2

AgGa_1-xIn_xS₂ with x=0.14±0.01 was found to be 90° phase-matchable for type-I difference-frequency generation (DFG) by mixing the dual-wavelength pulses emitted from an electronically tuned Ti:sapphire laser. Infrared radiation continuously tunable over the range of 4.80–6.98 μm was generated by independently varying the two wavelengths in the 705–932 nm spectral range, and 4.04 μm radiation by mixing a Nd:YAG laser with the Ti:sapphire laser. In addition, this material was found to be noncritically phase-matchable for the second harmonic generation (SHG) of CO₂ laser radiation at 10.591 μm at 203 °C. Sellmeier equations that reproduce well these experimental data are presented. PACS  42.65.-k; 42.65.ky