TY - JOUR
T1 - Directional Proton Transfer in the Reaction of the Simplest Criegee Intermediate with Water Involving the Formation of Transient H3O+
AU - Liu, Jinfeng
AU - Liu, Yanqing
AU - Yang, Jinrong
AU - Zeng, Xiao Cheng
AU - He, Xiao
N1 - Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/4/8
Y1 - 2021/4/8
N2 - The reaction of Criegee intermediates with water vapor has been widely known as a key Criegee reaction in the troposphere. Herein, we investigated the reaction of the smallest Criegee intermediate, CH2OO, with a water cluster through fragment-based ab initio molecular dynamics simulations at the MP2/aug-cc-pVDZ level. Our results show that the CH2OO-water reaction could occur not only at the air/water interface but also inside the water cluster. Moreover, more than one reactive water molecules are required for the CH2OO-water reaction, which is always initiated from the Criegee carbon atom and ends at the terminal Criegee oxygen atom via a directional proton transfer process. The observed reaction pathways include the loop-structure-mediated and stepwise mechanisms, and the latter involves the formation of transient H3O+. The lifetime of transient H3O+ is on the order of a few picoseconds, which may impact the atmospheric budget of the other trace gases in the actual atmosphere.
AB - The reaction of Criegee intermediates with water vapor has been widely known as a key Criegee reaction in the troposphere. Herein, we investigated the reaction of the smallest Criegee intermediate, CH2OO, with a water cluster through fragment-based ab initio molecular dynamics simulations at the MP2/aug-cc-pVDZ level. Our results show that the CH2OO-water reaction could occur not only at the air/water interface but also inside the water cluster. Moreover, more than one reactive water molecules are required for the CH2OO-water reaction, which is always initiated from the Criegee carbon atom and ends at the terminal Criegee oxygen atom via a directional proton transfer process. The observed reaction pathways include the loop-structure-mediated and stepwise mechanisms, and the latter involves the formation of transient H3O+. The lifetime of transient H3O+ is on the order of a few picoseconds, which may impact the atmospheric budget of the other trace gases in the actual atmosphere.
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U2 - 10.1021/acs.jpclett.1c00448
DO - 10.1021/acs.jpclett.1c00448
M3 - Article
C2 - 33784110
AN - SCOPUS:85104047004
SN - 1948-7185
VL - 12
SP - 3379
EP - 3386
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 13
ER -