A Gaussian-2 molecular orbital study of the reaction of CF3 with NO2

Two possible reaction paths of the reaction of CF3 with NO2 in their ground electronic states have been studied using the G2 molecular orbital method. CF3 and NO2 are predicted to form, exothermically, two intermediates 1 and 2 (−75.8 and −72.1 kcal mol−1). The decomposition of 2 to CF2O+FON is less favoured thermodynamically with respect to the decomposition of 1 to CF2O+FNO, and has a higher activation energy (37.5 and 26.9 kcal mol−1). FON is predicted to disappear readily from the reaction products, in line with the experiment that no gas-phase absorption spectrum of FON has been reported.