Nontraditional (Per)oxy Ring-Closure Paths in the Atmospheric Oxidation of Isoprene and Monoterpenes

In the atmospheric oxidation of organic compounds, free peroxy and oxy radicals play a crucial role. The
traditional view is that peroxy radicals react with NO or with other (hydro-)peroxy radicals, whereas oxy
radicals decompose, undergo a hydrogen shift, or react with O2. However, we show in this quantum chemical
and statistical-rate investigation that the presence of a double CC bond in many (per)oxy radicals formed
from isoprene and monoterpenes, the most abundant nonmethane hydrocarbons emitted into the atmosphere,
can result in hitherto neglected ring-closure isomerizations. These processes are shown to be competitive
under atmospheric conditions and can substantially alter the predicted oxidation products. As an illustration,
the major pathways in the OH-initiated oxidation of β-pinene are discussed. It is shown that the predominance
of the (per)oxy ring-closure routes offers a consistent rationalization for the “anomalously” low observed
yields of traditional-pathway oxidation products from this compound.