TY - JOUR

T1 - Atmospheric Oxidation of Hydroperoxy Amides

AU - Kjærgaard, Eva R.

AU - Møller, Kristian H.

AU - Kjaergaard, Henrik G.

N1 - Funding Information: We thank Jing Chen and Nanna Falk Christensen for their helpful discussions. This work was supported by funding from the Novo Nordisk Foundation Interdisciplinary Synergy Program (NNF19OC0057374) and VILLUM FONDEN (VIL50443), and computer time was provided by the High Performance Computing Centre at the University of Copenhagen. Publisher Copyright: © 2023 American Chemical Society.

PY - 2023

Y1 - 2023

N2 - Recently, hydroperoxy amides were identified as major products of OH-initiated autoxidation of tertiary amines in the atmosphere. The formation mechanism is analogous to that found for ethers and sulfides but substantially faster. However, the atmospheric fate of the hydroperoxy amides remains unknown. Using high-level theoretical methods, we study the most likely OH-initiated oxidation pathways of the hydroperoxy and dihydroperoxy amides derived from trimethylamine autoxidation. Overall, we find that the OH-initiated oxidation of the hydroperoxy amides predominantly leads to the formation of imides under NO-dominated conditions and more highly oxidized hydroperoxy amides under HO2-dominated conditions. Unimolecular reactions are found to be surprisingly slow, likely due to the restricting, planar structure of the amide moiety.

AB - Recently, hydroperoxy amides were identified as major products of OH-initiated autoxidation of tertiary amines in the atmosphere. The formation mechanism is analogous to that found for ethers and sulfides but substantially faster. However, the atmospheric fate of the hydroperoxy amides remains unknown. Using high-level theoretical methods, we study the most likely OH-initiated oxidation pathways of the hydroperoxy and dihydroperoxy amides derived from trimethylamine autoxidation. Overall, we find that the OH-initiated oxidation of the hydroperoxy amides predominantly leads to the formation of imides under NO-dominated conditions and more highly oxidized hydroperoxy amides under HO2-dominated conditions. Unimolecular reactions are found to be surprisingly slow, likely due to the restricting, planar structure of the amide moiety.

U2 - 10.1021/acs.jpca.3c04509

DO - 10.1021/acs.jpca.3c04509

M3 - Journal article

C2 - 37877667

AN - SCOPUS:85177839041

VL - 127

SP - 9311

EP - 9321

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 44

ER -