Trace concentrations of NO and NO<sub>2</sub> molecules are differentiated spectrally by using a visible dye laser and a simple flow cell with a pair of miniature electrodes for ion detection. NO is detected near 452 nm by (2+2) resonance-enhanced multiphoton ionization via its A<sup>2</sup>&Sigma;<sup>+</sup>-X<sup>2</sup>II (0,0) transitions, while NO<sub>2</sub> is detected by laser photofragmentation with subsequent fragment NO ionization via the A<sup>2</sup>&Sigma;<sup>+</sup>-X<sup>2</sup>II (0,0) and (1,1) transitions. Spectral differentiation is possible since the internal energy of the NO photofragment differs from that of "ambient" NO. Measurement of vibrationally excited NO via its A<sup>2</sup>&Sigma;<sup>+</sup>-X<sup>2</sup>II (0,3) band is also demonstrated at 517 nm. Rotationally resolved spectra of NO and fragment NO are analyzed by using a multiparameter computer program based on two-photon energy level expressions and line strengths for A<sup>2</sup>&Sigma;<sup>+</sup>-X<sup>2</sup>II transitions. Boltzmann analysis of the P<sub>12</sub> + O<sub>22</sub> branch of the (0,0) band reveals that the rotational temperature of fragment NO is approximately 500 K compared to room-temperature NO. Limits of detection [signal-to-noise (S/N) = 3] of NO and NO<sub>2</sub> are in the 20-40-ppbv range at 449.2, 450.7, and 452.6 nm for a 10-s integration time. The limit of detection of NO<sub>2</sub> at 517.5 nm is 75 ppbv. The analytical utility of the technique for ambient air analysis is evaluated and discussed.

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