Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces

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

Research output: Contribution to journalArticle

21 Citations (Scopus)

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.

Original languageEnglish (US)
JournalAngewandte Chemie - International Edition
DOIs
StateAccepted/In press - 2017

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Water
Proton transfer
Air
Molecular dynamics
Carbon
Hydrogen
Computer simulation

Keywords

  • Abinitio dynamics simulation
  • Air-water interface
  • Atmospheric chemistry
  • Criegee intermediate

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces. / Zhong, Jie; Kumar, Manoj; Zhu, Chong Q.; Francisco, Joseph S.; Zeng, Xiao C.

In: Angewandte Chemie - International Edition, 2017.

Research output: Contribution to journalArticle

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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.

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