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

Abstract

A SACM/CT study of the CF2(OH)CF2OO+NO2→CF2(OH)CF2OONO2 and CF3CF2OO+NO2→CF3CF2OONO2 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)0.37cm3molecule−1s−1 and 1.79×1016(T/300)0.40exp(−24.4kcalmol−1/RT)s−1 were derived at 200–300K for the direct and backward reactions of CF2(OH)CF2OONO2, while for CF3CF2OONO2, the expressions 1.01×10−12(T/300)0.39cm3molecule−1s−1 and 1.05×1016(T/300)0.44exp(−23.0kcalmol−1/RT)s−1 were obtained. A decomposition lifetime profile was derived for CF2(OH)CF2OONO2, indicating that it could act as transport and reservoir of CF2(OH)CF2OO and NO2 in the stratosphere.