Experimental and theoretical study of the recombination reaction FSO 2 + O 2 → FS(O 2)OO

• Published in: Chemical physics letters Vol. 465; no. 1; pp. 15 - 19
• Main Authors: Tucceri, M.E., Badenes, M.P., Croce, A.E., Cobos, C.J.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 2008
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2008.09.033

FSO 3 absorbance recorded at 450 nm following the 193 nm photolysis of FS(O 2)O(O 2)SF. The addition of O 2 modifies the decay due to the reaction FSO 2 + O 2 → FS(O 2)OO. The kinetics of the recombination reaction FSO 2 + O 2 → FS(O 2)OO (1) has been studied at 298 K. FSO 2 together with FSO 3 radicals were generated by 193 nm laser flash photolysis of FS(O 2)O(O 2)SF. The measured rate coefficient at one atmosphere total pressure is k 1 = (4.6 ± 0.6) × 10 −15 cm 3 molecule −1 s −1. Molecular properties for the FS(O 2)OO radical were calculated at the B3LYP/6-311+G(3df) and CCSD/6-311G(d) levels of theory. Consistent with the measured k 1 value, different density functional theory and G aussian-3 calculations predict an electronic energy barrier for reaction (1) close to 3 kcal mol −1.