The reaction of HO2+ formaldehyde is characterized at both the semiemp
irical and ab initio levels. It is shown that semiempirical methods do
not furnish the information necessary to rationalize the kinetics of
the formation of OOCH2OH. The mechanism of this reaction is rationaliz
ed at both the MP4/6-31G* and BAC MP4/6-31G** levels. The critical tr
ansition state for this reaction involves the simultaneous addition of
the terminal oxygen atom of HO2 to the carbon of the CO bond and tran
sfer of a proton from OOH to the oxygen of this same bond. It is shown
that the previously proposed mechanism involving the intermediate for
mation of the HOOCH2O radical is incorrect. Kinetic modeling indicates
that the critical transition state has an energy close to the incomin
g HO2 + CH2O channel and that a large deuterium isotope effect should
occur in the reaction of DO2 + CH2O.