Atmospheric Oxidation of Hydroperoxy Amides
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Atmospheric Oxidation of Hydroperoxy Amides. / Kjærgaard, Eva R.; Møller, Kristian H.; Kjaergaard, Henrik G.
I: Journal of Physical Chemistry A, Bind 127, Nr. 44, 2023, s. 9311-9321.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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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 -
ID: 376290893