Gas phase unimolecular decomposition and chemiluminescence of tetramethyldioxetane initiated by a tea CO2 laser

Time resolved chemiluminescence spectra of pure tetramethyldioxetane are obtained for the first time using pulsed infrared laser excitation. The only major product, acetone, is shown to be formed by at least two pathways: a unimolecular, collision free, decomposition and a collision induced mechanism. Spectral and temporal behaviour indicate that neither singlet nor triplet acetone are the primary products. Other possibilities are discussed.