Infrared laser-induced decomposition of 2,2-dimethyloxetane

The unimolecular decomposition of 2,2 dimethyloxetance to give either isobutence and formaldehyde or ethene and acetone induced by a pulsed CO₂ laser has been investigated. Absorption characteristics and fractional decomposition have been studied as a function of laser fluence, irradiation frequency, reactant pressure, and added inert bath gas. Both absorption cross section and fractional decomposition are approximately independent of pressure of 2,2-dimethyloxetane below 50 times; 10^?3 torr and increase with pressure at higher pressures of 2,2-dimethyloxetane. At pressures sufficiently low that collisions are negligible during the laser pulse, added inert gases reduce the amount of decomposition. Calculations of the fractional decomposition have been carried out based on RRKM theory and assuming either a Boltzmann or a Poisson intermolecular energy distribution. Master equation calculations of both absorption and decomposition for 10R20 irradiation have also been performed. Agreement between observed and calculated results for 10R20 irradiation could be obtained only by assuming that most, but not all, of the molecules in the irradiated volume absorb the laser radiation. Differences between the absorptions of the 10R20 and 9P20 lines and in the resulting extents of decomposition indicate that the fraction of irradiated molecules which absorbs 9P20 radiation is smaller than the fraction which absorbs 10R20 radiation.