TITLE

Coherent anti-Stokes Raman spectroscopy study of collisional broadening in the O2–H2O Q branch

AUTHOR(S)
Fanjoux, G.; Millot, G.; Saint-Loup, R.; Chaux, R.; Rosenmann, L.
PUB. DATE
July 1994
SOURCE
Journal of Chemical Physics;7/15/1994, Vol. 101 Issue 2, p1061
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The fundamental isotropic Raman Q branch of oxygen perturbed by collisions with water vapor has been studied at pressures up to 1.5 atm and for temperatures between 446 and 990 K. The spectra have been recorded by using coherent anti-Stokes Raman spectroscopy (CARS) which has been preferred to stimulated Raman spectroscopy (SRS) in order to obtain more signal and higher sensitivity as the mixture has a small percentage of oxygen. The high resolution CARS spectrometer uses a seeded Nd:YAG laser actively stabilized on an external Fabry–Perot interferometer to prevent any frequency drift during the course of the experiment. The line broadening coefficients have been determined for several rotational quantum numbers (up to N=31 at 990 K). The effect of the splitting into triplets at lower pressure and the effect of interferences between neighboring lines at higher pressure have been taken into account. The influence of Dicke narrowing has also been considered and special care has been taken to avoid Stark broadening. The line broadening coefficients have been calculated according to a semiclassical model. The rotational quantum number and temperature dependencies of the experimental line broadening coefficients have also been studied with another approach based on fitting and scaling laws. Among several laws, the modified exponential energy gap law (MEG), the statistical power-exponential gap law (SPEG), and the energy corrected sudden law with basis rate constants taken as a hybrid exponential-power law (ECS-EP) have given good results. We have used the fitting and scaling laws to extrapolate in temperature the linewidths at 2000 K.
ACCESSION #
7640038

 

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