Reactions with Criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere

Atmospheric oxidation processes are of central importance in atmospheric climate models. It is often considered that volatile organic molecules are mainly removed by hydroxyl radical; however, the kinetics of some reactions of hydroxyl radical with volatile organic molecules are slow. Here we report rate constants for rapid reactions of formyl fluoride with Criegee intermediates. These rate constants are calculated by dual-level multistructural canonical variational transition state theory with small-curvature tunneling (DL-MS-CVT/SCT). The treatment contains beyond-CCSD(T) electronic structure calculations for transition state theory, and it employs validated density functional input for multistructural canonical variational transition state theory with small-curvature tunneling and for variable-reaction-coordinate variational transition state theory. We find that the M11-L density functional has higher accuracy than CCSD(T)/CBS for the HC(O)F + CH₂OO and HC(O)<i>F</i> + <i>anti</i>-CH₃CHOO reactions. We find significant negative temperature dependence in the ratios of the rate constants for HC(O)F + CH₂OO/<i>anti</i>-CH₃CHOO to the rate constant for HC(O)<i>F</i> + OH. We also find that different Criegee intermediates have different rate-determining-steps in their reactions with formyl fluoride, and we find that the dominant gas-phase removal mechanism for HC(O)F in the atmosphere is the reaction with CH₂OO and/or <i>anti</i>-CH₃CHOO Criegee intermediates.