Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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Author(s)

  • Jie Zhong
  • Manoj Kumar
  • Chong Q. Zhu
  • Joseph S. Francisco
  • Xiao C. Zeng

Detail(s)

Original languageEnglish
Pages (from-to)7740-7744
Journal / PublicationAngewandte Chemie - International Edition
Volume56
Issue number27
Publication statusPublished - 26 Jun 2017
Externally publishedYes

Abstract

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.

Research Area(s)

  • ab initio dynamics simulation, air–water interface, atmospheric chemistry, Criegee intermediate

Bibliographic Note

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Citation Format(s)

Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces. / Zhong, Jie; Kumar, Manoj; Zhu, Chong Q. et al.
In: Angewandte Chemie - International Edition, Vol. 56, No. 27, 26.06.2017, p. 7740-7744.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review