Model, software and database for line-mixing effects in the ν3 and ν4 bands of CH4 and tests using laboratory and planetary measurements-I: N2(and air) broadenings and the earth atmosphere

International audience; Absorption spectra of the infrared ν3 and ν4 bands of CH4 perturbed by N2 over large ranges of pressure and temperature have been measured in the laboratory. A theoretical approach accounting for line mixing is proposed to (successfully) model these experiments. It is similar to that of Pieroni et al. [J Chem Phys 1999;110:7717–32] and is based on state-to-state rotational cross-sections calculated with a semi-classical approach and a few empirical parameters. The latter, which enable switching from the state space to the line space, are deduced from a fit of a single room temperature spectrum of the ν3 band at 50 atm. The comparisons between numerous measured and ca…

Model, software and database for line-mixing effects in the nu3 and nu4 bands of CH4 and tests using laboratory and planetary measurements - II : H2 (and He) broadening and the atmospheres of Jupiter and Saturn

International audience; The absorption shapes of the nu(2), nu(3) and nu(4) infrared bands of CH4 perturbed by H-2 in large ranges of pressure and temperature have been measured in the laboratory. In order to model these spectra, the theoretical approach accounting for line-mixing effects proposed for CH4-N-2 and CH4-air and successfully tested in the companion paper (1), is used. As before, state-to-state rotational rates are used together with some empirical parameters that are deduced from a fit of a single room temperature spectrum of the nu(3) band at about 50 atm. The comparisons between measured and calculated spectra in the nu(3) and nu(4) regions under a vast variety of conditions …

Temperature measurement in gas mixtures by femtosecond Raman-induced polarization spectroscopy

The potential of femtosecond Raman-induced polarization spectroscopy (RIPS) for the simultaneous determination of temperature and concentrations was investigated. These measurements were related to the rotational time response of the molecular gas mixture, which was measured as a function of the pump-probe time delay. The change of the polarizability anisotropy with respect to the vibrational levels was taken into account. The results of temperature measurements in pure CO2 showed good agreement with the values obtained by a thermocouple. The RIPS technique was also applied to a CO2-N2 gas mixture to determine simultaneously temperatures and concentrations at temperatures up to 600 K. The a…

MOLECULAR LINE-SHAPE MODELING FROM FIRST PRINCIPLES

International audience; We present an ab initio approach to spectral line-shape modeling and the comparison of the results with experimental data.

Determination of concentrations in ternary and quaternary molecular gas mixtures using femtosecond Raman spectroscopy

Measurements of concentrations in gas mixtures of three and four molecular components are presented. They rely on a femtosecond time-resolved pump–probe technique based on Raman-induced polarization spectroscopy. The rotational time response of the molecular gas mixture is measured as a function of the pump–probe time delay. No selective frequency tunability is needed as the molecular rotational spectra are excited within the laser bandwidth. The results obtained from experiments performed at room temperature in N2O–CO2–N2 and N2O–CO2–O2–N2 mixtures are presented and the accuracy of the method is discussed. Copyright © 2002 John Wiley & Sons, Ltd.

Spectroscopie Raman Anti-Stokes Cohérente femtoseconde (DRASC – fs) : expériences et modélisation dans le cas du mélange H2 – N2 à basse pression

Dans l'objectif du diagnostic de la temperature dans les milieux en combustion, la Diffusion Raman Anti-Stokes Coherente resolue en temps (DRASC - fs) est utilisee pour sonder H 2 dans les melanges H 2 -N 2 a basse pression. Le dispositif DRASC mis en place est decrit en detail. Un nouveau modele de la reponse DRASC temporelle, prenant en compte tous les effets collisionnels specifiques a l'hydrogene (effets dits « de vitesse ») est presentee, ainsi que la comparaison avec l'experience, l'accord se revelant tres satisfaisant.

Speed-memory effects in H2-N2 mixtures studied by CARS femtosecond. Experiments and modelization from the collisional to the Doppler regime

Femtosecond Raman time-resolved molecular spectroscopy

International audience; The applicability of several femtosecond time resolved non-linear coherent techniques such as Raman induced polarization spectroscopy (RIPS), degenerate four-wave mixing (DFWM) and coherent anti-Stokes Raman spectroscopy (CARS) for molecular spectroscopy is presented. All methods rely on the initial coherent excitation of molecular states producing wavepackets, whose time evolution is then measured. In the case of RIPS and DFWM only pure rotational transitions are involved, whereas in CARS vibrational states can be excited. First the methodology of concentration and temperature measurements using RIPS in gas mixtures involving N2, CO2, O2, and N2O is shown. In additi…

Femtosecond Raman time-resolved molecular spectroscopy

Abstract The applicability of several femtosecond time resolved non-linear coherent techniques such as Raman induced polarization spectroscopy (RIPS), degenerate four-wave mixing (DFWM) and coherent anti-Stokes Raman spectroscopy (CARS) for molecular spectroscopy is presented. All methods rely on the initial coherent excitation of molecular states producing wavepackets, whose time evolution is then measured. In the case of RIPS and DFWM only pure rotational transitions are involved, whereas in CARS vibrational states can be excited. First the methodology of concentration and temperature measurements using RIPS in gas mixtures involving N2, CO2, O2, and N2O is shown. In addition some applica…