TY - JOUR
T1 - Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces
AU - Zhong, Jie
AU - Kumar, Manoj
AU - Zhu, Chong Q.
AU - Francisco, Joseph S.
AU - Zeng, Xiao C.
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/6/26
Y1 - 2017/6/26
N2 - Criegee intermediates have implications as key intermediates in atmospheric, organic, and enzymatic reactions. However, their chemistry in aqueous environments is relatively unexplored. Herein, Born–Oppenheimer molecular dynamics (BOMD) simulations examine the dynamic behavior of syn- and anti-CH3CHOO at the air–water interface. They show that unlike the simplest Criegee intermediate (CH2OO), both syn- and anti-CH3CHOO remain inert towards reaction with water. The unexpected high stability of C2 Criegee intermediates is due to the presence of a hydrophobic methyl substituent on the Criegee carbon that lowers the proton transfer ability and inhibits the formation of a pre-reaction complex for the Criegee–water reaction. The simulation of the larger Criegee intermediates, (CH3)2COO, syn- and anti-CH2C(CH3)C(H)OO on the water droplet surface suggests that strongly hydrophobic substituents determine the reactivity of Criegee intermediates at the air–water interface.
AB - Criegee intermediates have implications as key intermediates in atmospheric, organic, and enzymatic reactions. However, their chemistry in aqueous environments is relatively unexplored. Herein, Born–Oppenheimer molecular dynamics (BOMD) simulations examine the dynamic behavior of syn- and anti-CH3CHOO at the air–water interface. They show that unlike the simplest Criegee intermediate (CH2OO), both syn- and anti-CH3CHOO remain inert towards reaction with water. The unexpected high stability of C2 Criegee intermediates is due to the presence of a hydrophobic methyl substituent on the Criegee carbon that lowers the proton transfer ability and inhibits the formation of a pre-reaction complex for the Criegee–water reaction. The simulation of the larger Criegee intermediates, (CH3)2COO, syn- and anti-CH2C(CH3)C(H)OO on the water droplet surface suggests that strongly hydrophobic substituents determine the reactivity of Criegee intermediates at the air–water interface.
KW - Criegee intermediate
KW - ab initio dynamics simulation
KW - air–water interface
KW - atmospheric chemistry
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U2 - 10.1002/anie.201702722
DO - 10.1002/anie.201702722
M3 - Article
C2 - 28471069
AN - SCOPUS:85018441035
SN - 1433-7851
VL - 56
SP - 7740
EP - 7744
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 27
ER -