Atmospheric Autoxidation of Amines.

Autoxidation has been acknowledged as a major oxidation pathway in a broad range of atmospherically important compounds including isoprene, monoterpenes, and very recently, dimethyl sulfide. Here, we present a high-level theoretical multiconformer transition-state theory study of the atmospheric autoxidation in amines exemplified by the atmospherically important trimethylamine (TMA) and dimethylamine and generalized by the study of the larger diethylamine. Overall, we find that the initial hydrogen shift reactions have rate coefficients greater than 0.1 s-1 and autoxidation is thus an important atmospheric pathway for amines. This autoxidation efficiently leads to the formation of hydroperoxy amides, a new type of atmospheric nitrogen-containing compounds, and for TMA, we experimentally confirm this. The conversion of amines to hydroperoxy amides may have important implications for nucleation and growth of atmospheric secondary organic aerosols and atmospheric OH recycling.