Concentration modulation spectroscopy with a pulsed slit supersonic discharge expansion source

Frequency modulated discharges are combined with pulsed slit supersonic expansions to provide an intense, long path source of jet-cooled radicals/molecular ions for direct absorption laser spectroscopy. The high modulation frequency (100 kHz) permits lock-in detection of the modulated absorbance signals at sensitivities down to 7.3×10−7 absorbance/Hz1/2 (within 40% of the shot noise limit) and provides excellent discrimination for radical or molecular ion spectra in the presence of much higher precusor concentrations. The sensitivity of these methods is demonstrated with direct absorption spectral data on sample jet-cooled molecular ions (H+3) and hydrocarbon radicals (CH3CH2).