New Mechanistic Pathways for Criegee-Water Chemistry at the Air/Water Interface

Chongqin Zhu, Manoj Kumar, Jie Zhong, Lei Li, Joseph S. Francisco, Xiao Cheng Zeng

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Understanding Criegee chemistry has become one of central topics in atmospheric research recently. The reaction of Criegee intermediates with gas-phase water clusters has been widely viewed as a key Criegee reaction in the troposphere. However, the effect of aerosols or clouds on Criegee chemistry has received little attention. In this work, we have investigated the reaction between the smallest Criegee intermediate, CH 2 OO, and water clusters in the gas phase, as well as at the air/water surface using ab initio quantum chemical calculations and adaptive buffered force quantum mechanics/molecular mechanics (QM/MM) dynamics simulations. Our simulation results show that the typical time scale for the reaction of CH 2 OO with water at the air/water interface is on the order of a few picoseconds, 2-3 orders of magnitude shorter than that in the gas phase. Importantly, the adbf-QM/MM dynamics simulations suggest several reaction pathways for the CH 2 OO + water reaction at the air/water interface, including the loop-structure-mediated mechanism and the stepwise mechanism. Contrary to the conventional gas-phase CH 2 OO reaction, the loop-structure is not a prerequisite for the stepwise mechanism. For the latter, a water molecule and the CH 2 OO at the air/water interface, upon their interaction, can result in the formation of (H 3 O) + and (OH)CH 2 (OO) - . Thereafter, a hydrogen bond can be formed between (H 3 O) + and the terminal oxygen atom of (OH)CH 2 (OO) - , leading to direct proton transfer and the formation of α-hydroxy methylperoxide, HOCH 2 OOH. The mechanistic insights obtained from this simulation study should motivate future experimental studies of the effect of water clouds on Criegee chemistry.

Original languageEnglish (US)
Pages (from-to)11164-11169
Number of pages6
JournalJournal of the American Chemical Society
Volume138
Issue number35
DOIs
StatePublished - Sep 7 2016

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Air
Water
Mechanics
Gases
Molecular mechanics
Quantum theory
Molecular Dynamics Simulation
Troposphere
Proton transfer
Computer simulation
Aerosols
Protons
Hydrogen
Hydrogen bonds
Oxygen
Atoms
Molecules
Research

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

New Mechanistic Pathways for Criegee-Water Chemistry at the Air/Water Interface. / Zhu, Chongqin; Kumar, Manoj; Zhong, Jie; Li, Lei; Francisco, Joseph S.; Zeng, Xiao Cheng.

In: Journal of the American Chemical Society, Vol. 138, No. 35, 07.09.2016, p. 11164-11169.

Research output: Contribution to journalArticle

Zhu, Chongqin ; Kumar, Manoj ; Zhong, Jie ; Li, Lei ; Francisco, Joseph S. ; Zeng, Xiao Cheng. / New Mechanistic Pathways for Criegee-Water Chemistry at the Air/Water Interface. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 35. pp. 11164-11169.
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