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MULTI GAS SENSING BASED ON PHOTOACOUSTIC SPECTROSCOPY BY USING TUNABLE DIODE LASERS
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A3.MULTI GAS SENSING BASED ON PHOTOACOUSTIC SPECTROSCOPY BY USING TUNABLE DIODE LASERS J-Ph. Besson, S. Schilt, L. Thévenaz, P. Robert EPFL, Swiss Federal Institute of Technology Laboratory of metrology and photonicsCH-1015 Lausanne, Switzerland Contact Address: jean-philippe.besson@epfl.ch Gas sensing using resonant photoacoustic spectroscopy has been proved to be a very good technique for low concentration measurements. In this work, we present a gas sensor capable to measure three substances simultaneously that are unwanted hydrogen precursors in fibre optics manufacturing. Water vapour (H2O), methane (CH4) and hydrogen chloride (HCl) at wavelength of 1368.6 nm, 1651.0 nm and 1742.4 nm respectively are measured with DFB tunable laser diodes. The coupling of the wavelengths is achieved by using optical fibres terminated with a collimator to launch the light directly into the photoacoustic cell. The resonant photoacoustic cell is designed to operate on the first longitudinal acoustic mode. The optimisation of the cell constant to achieving the best acoustic signal is obtained by varying the geometric dimensions (radius and length) of the cell. Simulations show that the radius should be as small as possible and that the length should be as long as possible. In addition to those two parameters the resonant frequency and the volume must be reasonable (frequency must be greater than 1 KHz to avoid 1/f noise). A critical comparison between the simulations and the real cell will be presented. First results show that a sensitivity of 0.3 ppm for water vapour, 0.4 ppm for hydrogen chloride and 1 ppm for methane can be obtained for such a cell.
A4.Collisional Broadening Analysis by Diode-Laser Spectroscopy: PH3 + H2. Gh. Blanquet, J. Walrand Laboratoire de Spectroscopie Moléculaire FUNDP, 61, rue de Bruxelles, B-5000, Belgium. J. Salem, H Aroui Laboratoire de Physique Moléculaire, Ecole Supérieure des Sciences et Techniques de Tunis, 5 Avenue Taha Hussein, 1008 Tunis, Tunisia J.P. Bouanich a Laboratoire de Photophysique Moléculaire, CNRS, Université de Paris-Sud, Bâtiment 350, F-91405 Orsay cedex, France Phosphine is a molecule of astrophysical interest since it has been observed in the atmosphere of Jupiter and Saturn which is mainly composed of hydrogen and helium. Therefore the determination of H2-broadening coefficients of PH3 may be useful in modeling planetary atmospheres. H2-broadening coefficients are measured for 41 lines of PH3 in the QR branch of the 2 band and the PP, RP, and PQ branches of the -4 band, using a tunable diode-laser spectrometer. The recorded lines with J values ranging from 2 to 16 and K from 0 to 11 are located between 995 and 1106 cm-1. The collisional widths are determined by fitting each spectral line with a Voigt profile, a Rautian profile, and a speed-dependent Rautian profile. The latter model provides slightly larger broadening coefficients than the Voigt model. These coefficients are also calculated on the basis of a semiclassical model of interacting linear molecules, using an atom-atom Lennard-Jones potential in addition to the weak electrostatic contributions. The theoretical results are in satisfactory agreement with the experimental data, except for the QR(J,K) transitions with K = J, where they are notably underestimated.
A5.Line frequency shift measurements by diode-laser spectroscopy for CH3D-Xe Ch. Lerot, Gh. Blanquet, J. Walrand, M. Lepère* Laboratoire de Spectroscopie Moléculaire, FUNDP, 61, rue de Bruxelles,B-5000 Namur, Belgium J.P. Bouanich Laboratoire de Photophysique Moléculaire, CNRS, Université de Paris-Sud, Bâtiment 350, F-91405 Orsay cedex, France. If numerous studies on the collisional line broadening have been realized by diode-laser spectroscopy only a few papers are devoted to the measurements of collisional shifts. Indeed, the frequency shift of lines also due to collisions between molecules is a much weaker effect than the collisional broadening and is difficult to measure accurately. In the case of symmetric top molecules, the system of CH3D in collision with Xe is well suited to the study of line shifts. First the perturber mass is greater than the absorber mass which leads to larger shifts. Moreover the lines of CH3D are generally well isolated so that our measurements are not perturbed by the wings of neighbouring lines, even for high pressures of xenon. In this work, we have measured the shift coefficients for 5 lines [QP(7,4), QR(6,4), QR(10,2), QR(10,7), QR(12,4)] belonging to the 3 band of 12CH3D broadened by Xe at room temperature, using our tunable diode-laser spectrometer (1). To measure the shift of one line, we recorded the transmitted signal passing successively through two cells: the first filled with a very low pressure of CH3D and small absorption (our reference line) and the second containing the gas mixture, CH3D diluted by Xenon at four pressures between 350 and 600 mbar. A small unshifted line is then superposed near the summit of the pressure-broadened line. The shift coefficient was determined by fitting simultaneously a Voigt profile for the reference line and a Voigt or a Rautian profile for the broadened line.
A6.Absolute Line Intensity Measurements by Diode-Laser Spectroscopy: Hot Bands of OCS J. Walrand, M. Lengelé, Gh. Blanquet Laboratoire de Spectroscopie Moléculaire FUNDP, 61, rue de Bruxelles, B-5000, Belgium High resolution spectroscopy allows detection of individual vibration rotation lines from absorbing molecules of terrestrial and planetary atmospheres. Thus, it is important to have a good knowledge of the frequencies, profiles, and intensities of spectral lines determined from laboratory data to analyze astrophysical observations including absorption bands of minor constituents. Infrared measurements on OCS are of particular interest to measure the concentration of this molecule in the atmosphere. In last decades, some papers related to spectral intensities determined line by line have been published for transitions issued from the ground state levels (cold bands). For hot bands, only strengths of a few lines of the 1110 0110 transition (1) and of the 0200 0110 transition (2) were measured. The aim of this work is to report extensive measurements of lines belonging to the first hot bands associated with the fundamental 1 band near 850 cm-1. With a diode-laser spectrometer, we have recorded 58 lines for the e and f sub bands of the  band and 36 lines for the  band. The method of the equivalent width has been used to determine individual line strengths. Values for the band intensities and the transition dipole moments were deduced from the measured data.
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