Primary Formation of Highly Oxidized Multifunctional Products in the OH-Initiated Oxidation of Isoprene: A Combined Theoretical and Experimental Study

It is generally assumed that isoprene-derived secondary organic aerosol (SOA) precursors are mainly formed from the secondary reactions of intermediate products with OH radicals in the gas phase and multiphase oxidation in particles. In this paper, we predicted a theoretical mechanism for the primary formation of highly oxygenated molecules (HOM) in the gas phase through successive intramolecular H-shifts and O₂ addition in the specific Z-δ isomer of hydroxyl-peroxy radicals and alkoxy radicals. The position of O₂ addition is different from that in forming hydroperoxy aldehydes. The prediction was further supported experimentally by successfully identifying a few highly oxidized peroxy radicals and closed-shell products such as C₅H₉O_7,9, C₅H₁₀O_6,7,8, and C₄H₈O₅ in a flow reactor by chemical ionization mass spectrometry at air pressure. These HOM products could serve as important precursors to isoprene-derived SOA. Further modeling studies on the effect of NO concentration suggested that HOM formation could account for up to ∼11% of the branching ratio (∼9% from the 4-OH channel and ∼2% from the 1-OH channel) in the reaction of isoprene with OH when the lifetimes of peroxy radicals due to bimolecular reactions are ∼100 s, which is typical in forest regions.