Observation of Light-Induced Reactions of Olefin–Ozone Complexes in Cryogenic Matrices Using Fourier-Transform Infrared Spectroscopy

Each olefin (ethylene, trans-1,3-butadiene, isoprene, dimethyl butadiene (DMB)) and ozone molecules were codeposited on a CsI window at cryogenic temperature, and the products of photolysis with ultraviolet–visible light were observed using Fourier-transform infrared spectroscopy. The products of the C2H4–O3 system could be assigned to glyoxal (CHO–CHO), ethylene oxide (c–C2H4O), CO, and CO2. The formation of CHO–CHO and c–C2H4 and the absence of H2CO and HCOOH indicated that the main reaction channels did not involve C–C bond breaking. Based on this simple scheme, the photoproducts of different olefin–O3 systems were assigned, and the vibrational features predicted by density functional theory calculations were compared with the observed spectra. Regarding butadiene, spectral matches between the observations and calculations seemed reasonable, while assignments for isoprene ambiguities of and DMB remain, mainly because of the limited availability of authentic sample spectra.