| Autor: |
Lily, Makroni1 (AUTHOR), Lv, Xiaofan1 (AUTHOR), Chandra, Asit K.2 (AUTHOR) akchandra@nehu.ac.in, Tsona Tchinda, Narcisse1 (AUTHOR), Du, Lin1 (AUTHOR) lindu@sdu.edu.cn |
| Předmět: |
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| Zdroj: |
Environmental Science: Processes & Impacts. Apr2024, Vol. 26 Issue 4, p751-764. 14p. |
| Abstrakt: |
In this work, we have investigated the mechanism, thermochemistry and kinetics of the reaction of syn–cis-CH2＝RzCRyC＝O+O− (where Rz, Ry = H, CH3–) unsaturated Criegee intermediates (CIs) with CF3COOH using quantum chemical methods. The rate coefficients for the barrierless reactions were calculated using variable reaction coordinate variational transition state theory (VRC-VTST). For the syn–cis-CH2＝RzCRyC＝O+O− conformation in which conjugated C＝C and C＝O double bonds are aligned with each other, we propose a new pathway for the unidirectional addition of an O＝C–OH molecule (CF3COOH) to the C＝C double bond of syn–cis-CH2＝RzCRyC＝O+O−. The rate coefficient for the 1,4-C＝C addition reaction at 298 K is ∼10−10 to 10−11 cm3 s−1, resulting in the formation of CF3C(O)OCH2CRz＝RyCOOH trifluoroacetate alkyl allyl hydroperoxide (TFAAAH) as a new transitory adduct. It can act as a precursor for the formation of secondary organic aerosols (SOAs). This novel TFAAAH hydroperoxide was identified through a detailed quantum chemical study of the 1,4-addition mechanism and will provide new insights into the significance of the 1,4-addition reaction of unsaturated Cls with trace tropospheric gases on –CRz＝CH2 vinyl carbon atoms. [ABSTRACT FROM AUTHOR] |
| Databáze: |
GreenFILE |
| Externí odkaz: |
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