Formation and dissociation kinetics of the FC(O)OOO(O)CF, FS(O2)OOO(O2)SF and FC(O)OOO(O2)SF trioxides. A theoretical study

Abstract A SACM/CT study of the FC(O)O + FC(O)OO → FC(O)OOO(O)CF, FS(O 2 )O + FS(O 2 )OO → FS(O 2 )OOO(O 2 )SF, FC(O)OO + FS(O 2 )O → FC(O)OOO(O 2 )SF and FC(O)O + FS(O 2 )OO → FC(O)OOO(O 2 )SF recombination reactions and their reverse dissociation processes was performed. The electronic energy along the reaction pathways was calculated at the G3S(MP2)//B3LYP/6-311+G(3df) level of theory. The respective high pressure rate coefficients obtained at 298 K are 3.2 × 10 −12 , 4.3 × 10 −13 , 8.5 × 10 −13 , 1.1 × 10 −12  cm 3  molecule −1  s −1 . The first calculated value compares very well with the available experimental one. From the corresponding thermal dissociation rate coefficients, lifetimes of about 170 days, 4 days and 1 min are predicted for FC(O)OOO(O)CF, FC(O)OOO(O 2 )SF and FS(O 2 )OOO(O 2 )SF.