A neglected pathway for the accretion products formation in the atmosphere

Highly oxygenated organic molecules (HOM) formed by the autoxidation of α-pinene initiated by OH radicals play an important role in new particle formation. It is believed that the accretion products, ROOR´, formed by the self- and cross-reaction of peroxy radicals (RO₂ + R'O₂ reactions), have extremely low volatility and are more likely to participate in nucleation. However, the mechanism of ROOR´ formation has not been fully demonstrated by experiment or theoretical calculation. Herein, we propose a novel mechanism of RO₂ reacting with α-pinene (RO₂ + α-pinene reactions) that have much lower potential barriers and larger rate constants than the reaction of RO₂ with R'O₂, which explains the ROOR´ formation found in the mass spectrometry experiments. The ROOR´ resulting from the reaction of RO₂ with α-pinene can produce HOM dimers and trimers with a higher oxygen-to‑carbon (O/C) ratio through a autoxidation chain. We also demonstrated that the presence of NO_x and HO₂ radical will reduce the RO₂ concentration, but cannot completely inhibit the formation of HOM monomers and ROOR´. Even if one or both of RO₂ radicals are acyl peroxy radicals (RC(O)O₂), the potential barriers of the reactions between RC(O)O₂ and α-pinene (RC(O)O₂ + α-pinene reactions) are lower than that of RO₂ reacting with RC(O)O₂ (RO₂ + RC(O)O₂ reactions) or RC(O)O₂ self-reactions (RC(O)O₂ + RC(O)O₂ reactions). The current work revealed, for the first time, a mechanism of RO₂/RC(O)O₂ reacting with α-pinene in the atmosphere, which provides new insight into the atmospheric chemistry of accretion products as SOA precursors.