Photofragmentation-laser induced fluorescence: a new method for detecting atmospheric trace gases.

A new method for the in situ detection of nonfluorescing molecular species is proposed: photofragmentation-laser induced fluorescence (PF-LIF). In this approach, the species to be detected is first laser photolyzed at a wavelength lambda(1), producing one or more vibrationally excited photofragments. Before vibrational relaxation occurs, one of these photofragments is pumped into a bonding excited state by a second laser pulse centered at wavelength lambda (2). Fluorescence is sampled at a wavelength lambda (3), where lambda (3) < lambda(2) and lambda(1) This pumping configuration thus permits massive discrimination against Rayleigh and Raman scattering as well as white noise fluorescence from the laser wavelengths lambda(1) and lambda(2). The technique should be both highly sensitive and selective for numerous atmospheric trace gases. Specific sampling schemes for detecting NO(2), NO(3), and HNO(2) are proposed. Various noise sources and chemical interferences are discussed. Specific calculations that estimate the sensitivity of the PF-LIF system for detecting NO(2), NO(3), and HNO(2) are given.