Theoretical study on the mechanism of reaction of CHF2 with NO2

► The reaction mechanism of CHF2 with NO2 is explored at the DFT, ab initio levels. ► The H-migration channel leading to P1 (CF2 + HONO) is the most favorable pathway. ► The reaction rates of CH3−nFn + NO2 (n = 1, 2 and 3) are compared. ► The title reaction can be an effective method of NO2-reduction in atmospheric chemistry.