The Criegee intermediate-formic acid reaction explored by rotational spectroscopy

The atmospheric reaction of the simplest Criegee intermediate, CH2OO, with formic acid has been investigated in the gas phase by pulsed Fourier-transform microwave spectroscopy. The dominant nascent product from this reaction was identified as hydroperoxymethyl formate (HOOCH2OCHO), for which two different conformations, formed through independent insertion mechanisms, were observed in the discharged plasma of a CH2I2/O-2/formic acid gas mixture. The conformational identifications are supported by the observation of C-13 species in natural abundance together with the chemically mono substituted deuterium isotopologues. These isotopic observations further suggest that hydroperoxymethyl formate slightly decomposes, producing formic anhydride (OHCOCHO) in a dehydration reaction.