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New insights into the mechanism and kinetics of the addition reaction of unsaturated Criegee intermediates to CF3COOH and tropospheric implications
Environmental Science: Processes & Impacts ( IF 4.3 ) Pub Date : 2024-02-16 , DOI: 10.1039/d3em00554b Makroni Lily 1 , Xiaofan Lv 1 , Asit K Chandra 2 , Narcisse Tsona Tchinda 1 , Lin Du 1
Environmental Science: Processes & Impacts ( IF 4.3 ) Pub Date : 2024-02-16 , DOI: 10.1039/d3em00554b Makroni Lily 1 , Xiaofan Lv 1 , Asit K Chandra 2 , Narcisse Tsona Tchinda 1 , Lin Du 1
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In this work, we have investigated the mechanism, thermochemistry and kinetics of the reaction of syn–cis-CH2![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
RzCRyCO+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-CH2RzCRyCO+O− conformation in which conjugated CC and CO double bonds are aligned with each other, we propose a new pathway for the unidirectional addition of an OC–OH molecule (CF3COOH) to the CC double bond of syn–cis-CH2RzCRyCO+O−. The rate coefficient for the 1,4-CC addition reaction at 298 K is ∼10−10 to 10−11 cm3 s−1, resulting in the formation of CF3C(O)OCH2CRzRyCOOH 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 –CRzCH2 vinyl carbon atoms.
更新日期：2024-02-16
RzCRyCO+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-CH2RzCRyCO+O− conformation in which conjugated CC and CO double bonds are aligned with each other, we propose a new pathway for the unidirectional addition of an OC–OH molecule (CF3COOH) to the CC double bond of syn–cis-CH2RzCRyCO+O−. The rate coefficient for the 1,4-CC addition reaction at 298 K is ∼10−10 to 10−11 cm3 s−1, resulting in the formation of CF3C(O)OCH2CRzRyCOOH 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 –CRzCH2 vinyl carbon atoms.
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