Atmospheric Oxidation of Hydroperoxy Amides

Eva R Kjærgaard; Kristian H Møller; Henrik G Kjaergaard

doi:10.1021/acs.jpca.3c04509

Atmospheric Oxidation of Hydroperoxy Amides

Eva R Kjærgaard, Kristian H Møller, Henrik G Kjaergaard

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

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Abstract

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.

Originalsprog	Engelsk
Tidsskrift	The journal of physical chemistry. A
Vol/bind	127
Nummer	44
Sider (fra-til)	9311-9321
Antal sider	11
ISSN	1089-5639
DOI	https://doi.org/10.1021/acs.jpca.3c04509
Status	Udgivet - 9 nov. 2023
Udgivet eksternt	Ja

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title = "Atmospheric Oxidation of Hydroperoxy Amides",

abstract = "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.",

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TY - JOUR

T1 - Atmospheric Oxidation of Hydroperoxy Amides

AU - Kjærgaard, Eva R

AU - Møller, Kristian H

AU - Kjaergaard, Henrik G

PY - 2023/11/9

Y1 - 2023/11/9

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.

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U2 - 10.1021/acs.jpca.3c04509

DO - 10.1021/acs.jpca.3c04509

M3 - Journal article

C2 - 37877667

SN - 1089-5639

VL - 127

SP - 9311

EP - 9321

JO - The journal of physical chemistry. A

JF - The journal of physical chemistry. A

IS - 44

ER -

Atmospheric Oxidation of Hydroperoxy Amides

Abstract

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