Ozonolysis, the mechanism by which alkenes are oxidized by ozone in the atmosphere, produces a diverse family of oxidants known as Criegee intermediates (CIs). Using a combination of newly acquired laboratory data and global atmospheric chemistry and transport modeling, we find that the reaction of CIs with alcohols, a reaction that was originally employed to trap these reactive species and provide evidence for the ozonolysis mechanism nearly 70 years ago, is occurring in Earth’s atmosphere and may represent a sizable source of functionalized hydroperoxides therein. Rate coefficients are reported for the reactions of CH2OO and (CH3)2COO with methanol and that of CH2OO with ethanol. Substitution about the Criegee intermediate is found to have a strong influence over the reaction rate, whereas substitution on the alcohol moiety does not. Although these reactions are not especially rapid, both the precursors to CIs and alcohols have large emissions from the terrestrial biosphere, leading to a high degree of co-location for this chemistry. We estimate that the products of these reactions, the α-alkoxyalkyl hydroperoxides (AAAHs) have a production rate of ∼30 Gg year–1. To assess the atmospheric lifetime of AAAHs, we used the nuclear ensemble method to construct a UV absorption spectrum from the four lowest energy conformers identified for a representative AAAH, methoxymethyl hydroperoxide. The computed absorption cross-section indicates that these compounds will be lost by solar photolysis, although not so rapidly as to exclude competition from other sinks such as oxidation, thermal decay, and aerosol uptake.

High-level ab initio calculations (DF-LCCSD­(T)-F12a//B3LYP/aug-cc-pVTZ) are performed on a range of stabilized Criegee intermediate (sCI)–alcohol reactions, computing reaction coordinate energies, leading to the formation of α-alkoxyalkyl hydroperoxides (AAAHs). These potential energy surfaces are used to model bimolecular reaction kinetics over a range of temperatures. The calculations performed in this work reproduce the complicated temperature-dependent reaction rates of CH2OO and (CH3)2COO with methanol, which have previously been experimentally determined. This methodology is then extended to compute reaction rates of 22 different Criegee intermediates with methanol, including several intermediates derived from isoprene ozonolysis. In some cases, sCI–alcohol reaction rates approach those of sCI–(H2O)2. This suggests that in regions with elevated alcohol concentrations, such as urban Brazil, these reactions may generate significant quantities of AAAHs and may begin to compete with sCI reactions with other trace tropospheric pollutants such as SO2. This work also demonstrates the ability of alcohols to catalyze the 1,4-H transfer unimolecular decomposition of α-methyl substituted sCIs.