Formation, thermal decomposition and atmospheric implications of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates. A theoretical study

Abstract A SACM/CT study of the CF 2 (OH)CF 2 OO + NO 2  → CF 2 (OH)CF 2 OONO 2 and CF 3 CF 2 OO + NO 2  → CF 3 CF 2 OONO 2 recombination reactions and their reverse unimolecular decomposition process was performed. The electronic energy along the reaction pathways was calculated at the G4(MP2) level. High-pressure rate coefficients of 1.53 × 10 −12  (T/300) 0.37  cm 3  molecule −1  s −1 and 1.79 × 10 16  (T/300) 0.40  exp(−24.4 kcal mol −1 /RT) s −1 were derived at 200–300 K for the direct and backward reactions of CF 2 (OH)CF 2 OONO 2 , while for CF 3 CF 2 OONO 2 , the expressions 1.01 × 10 −12  (T/300) 0.39  cm 3  molecule −1  s −1 and 1.05 × 10 16  (T/300) 0.44  exp(−23.0 kcal mol −1 /RT) s −1 were obtained. A decomposition lifetime profile was derived for CF 2 (OH)CF 2 OONO 2 , indicating that it could act as transport and reservoir of CF 2 (OH)CF 2 OO and NO 2 in the stratosphere.