Femtosecond polarization spectroscopy in molecular gas mixtures: Macroscopic interference and concentration measurements

Abstract

Raman-induced polarization spectroscopy (RIPS) experiments combined with homodyne detection have been conducted with a femtosecond laser at room temperature and low pressure (p<2 atm) in CO2–N2 mixtures as well as in air (O2–N2 mixtures). Each molecule of the mixture produces its own time-dependent signal, measured as a series of recurring transients. Macroscopic interference is observed when transients of both molecules overlap in the time domain. This interference leads to a large modification of the signal, which is well reproduced by calculations. The total signal recorded in CO2–N2 or O2–N2 mixtures of known concentration is analyzed in order to measure the polarizability anisotropy ratio of the two components at 800 nm. The ratio measured in an O2–N2 (air) mixture is compared with values of previous works. The knowledge of the ratio for CO2/N2 allows us to determine the concentration of CO2–N2 unknown gas mixtures. The method is presented as a relevant technique for concentration measurements in the picosecond time domain. The accuracy of the measurements and the influence of macroscopic interference in the results are discussed. The present work can be easily extended to other gas mixtures and a broad concentration range.