Trace gas detection of molecular hydrogen H2 by photoacoustic stimulated Raman spectroscopy (PARS)

Abstract

Photoacoustic stimulated Raman spectroscopy (PARS) has been used for sensitive and selective trace gas detection of molecular hydrogen under ambient conditions. In one experiment, 532 nm output of a seeded pulsed Nd:YAG laser is employed as Raman pump source and a Raman shifter filled with gaseous H₂ to obtain Stokes shifted radiation at 683 nm, suitable to stimulate H₂ Raman detection in a photoacoustic cell. A noise equivalent detection limit of 40 ppm by volume H₂ in 1 atm N₂ is obtained (14 mJ at 532 nm, 18 mJ at 683 nm, 10 Hz repetition rate, 58 s measurement time). Another experiment employs a dye laser for stimulating Raman radiation between 681–684 nm, allowing tuneable PARS. A Gaussian spectral fitting procedure has been applied giving a noise equivalent detection limit of 4.6 ppm by volume H₂ in 1 atm N₂ (35 mJ pulse energy at 532 nm, 45 mJ at 681–684 nm, 10 Hz repetition rate, 256 s measurement time). Spectroscopic detection offers the advantage of high selectivity along with the ability to obtain temperature and dynamic information from the rotational population and a line shape analysis, and also allows the discrimination between ortho- and para-H₂.