Laser-induced photofragmentation with fragment ionization is used to detect and spectrally differentiate trace concentrations of NO₂ from NO in NO–NO₂ mixtures. A laser operating near 226 or 452 nm ionizes the target molecules, and the resulting electrons are collected with miniature electrodes. NO is detected by (1 + 1) resonance-enhanced multiphoton ionization by means of its A²Σ⁺ ← X²Π (0, 0) transitions near 226 nm, whereas NO₂ is detected near 226 nm by laser photofragmentation with subsequent NO fragment ionization by means of both its A²Σ⁺ ← X²Π (0, 0) and (1, 1) transitions. The NO fragment generated from the photolysis of NO₂ is produced rovibrationally excited with a significant population in the first vibrational level of the ground electronic state (X²Π, υ″ = 1). In contrast, ambient NO has a room-temperature, Boltzmann population distribution favoring the lowest ground vibrational level (X²Π, υ″ = 0). Thus discrimination is possible when the internal energy distributions of both fragment NO and ambient NO are probed. We also demonstrate this approach using visible radiation, further simplifying the experimental apparatus because frequency doubling of the laser radiation is not required. We measured up to three decades of NO–NO₂ mixtures with limits of detection (signal-to-noise ratio of 3) in the low parts per billion for both NO and NO₂ for a 10-s integration time using both ultraviolet or visible radiation.

© 2000 Optical Society of America

[Optical Society of America ]

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