Secondary Organic Aerosol Formation via the Isolation of Individual Reactive Intermediates: Role of Alkoxy Radical Structure

The study of the chemistry underlying secondary organic aerosol (SOA) formation is complicated by the large number of reaction pathways and oxidation generations available to a given precursor species. Here we simplify such complexity to that of a single alkoxy radical (RO), by forming SOA via the direct photolysis of alkyl nitrite (RONO) isomers. Chamber experiments were conducted with 11 C₁₀ RONO isomers to determine how the position of the radical center and branching of the carbon skeleton influences SOA formation. SOA yields served as a probe of RO reactivity, with lower yields indicating that fragmentation reactions dominate and higher yields suggesting the predominance of RO isomerization. The largest yields were from straight-chain isomers, particularly those with radical centers located toward the terminus of the molecule. Trends in SOA yields can be explained in terms of two major effects: (1) the relative importance of isomerization and fragmentation reactions, which control the distribution of products, and (2) differences in volatility among the various isomeric products formed. Yields from branched isomers, which were low but variable, provide insight into the degree of fragmentation of the alkoxy radicals; in the case of the two β-substituted alkoxy radicals, fragmentation appears to occur to a greater extent than predicted by structure–activity relationships. Our results highlight how subtle differences in alkoxy radical structure can have major impacts on product yields and SOA formation.