The infrared multiphoton dissociation of CF2HCl is investigated by monitoring the appearance of the CF2 product in real time during and after the laser pulse. The difluorocarbene radicals are detected quantitatively by their optical absorption in the ? 1B1←? 1A1 band system around 250 nm. The fragmentation is studied under collision-free conditions as well as in the presence of up to 500 Torr Ar.

The multiphoton dissociation of 32SF6 at 10.59 μm has been studied as a function of the temperature between 223 and 413 K. The observed decrease of the reaction yield with increasing temperature varies strongly with the laser energy fluence at the applied conditions. Rate constants for the unimolecular decomposition of sulfur hexafluoride induced by the monochromatic infrared radiation are derived at 223, 293, and 343 K.

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The application of 14 kG magnetic field greatly increased the multiphoton dissociation yield of CF2HCl. This effect is attributed to the breakdown of angular momentum selection rules. (AIP)

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