Investigation of the thermal and photochemical reactions of ozone with styrene in argon and krypton matrices

The matrix isolation technique, combined with infrared spectroscopy and twin jet codeposition, has been used to characterize intermediates formed during the ozonolysis of styrene. Absorptions assigned to early intermediates grew in after warming the matrix from 19 K to 68 K in the twin jet krypton matrix experiments. A number of these absorptions have been assigned to the primary ozonide, formaldehyde-O-oxide Criegee intermediate, and secondary ozonide of styrene, transient species not previously observed for this system. In contrast, the room temperature reaction of ozone with styrene led to the observation of “late,” stable products of this ozonolysis reaction. These product absorptions were observed after merged jet deposition, followed by cryogenic trapping in solid argon. Irradiation with λ ⩾ 220 nm of merged and twin jet argon matrices involving ozone led to O atom production and subsequent reaction with styrene. Identification of intermediates formed during the ozonolysis of styrene was further supported by 18O isotopic labeling experiments as well as theoretical density functional calculations at the B3LYP/6-311G++(d,2p) level.