Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway

We describe the products of the reaction of the hydroperoxy radical (HO2) with the alkylperoxy radical formed following addition of the nitrate radical (NO3) and O2 to isoprene. NO3 adds preferentially to the C1 position of isoprene (>6 times more favorably than addition to C4), followed by the addition of O2 to produce a suite of nitrooxy alkylperoxy radicals (RO2). At an RO2 lifetime of ∼30 s, δ-nitrooxy and β-nitrooxy alkylperoxy radicals are present in similar amounts. Gas-phase product yields from the RO2 + HO2 pathway are identified as 0.75–0.78 isoprene nitrooxy hydroperoxide (INP), 0.22 methyl vinyl ketone (MVK) + formaldehyde (CH2O) + hydroxyl radical (OH) + nitrogen dioxide (NO2), and 0–0.03 methacrolein (MACR) + CH2O + OH + NO2. We further examined the photochemistry of INP and identified propanone nitrate (PROPNN) and isoprene nitrooxy hydroxyepoxide (INHE) as the main products. INHE undergoes similar heterogeneous chemistry as isoprene dihydroxy epoxide (IEPOX), likely contributing to atmospheric secondary organic aerosol formation.