Criegee intermediate-hydrogen sulfide chemistry at the air/water interface

Authors

Manoj Kumar, University of Nebraska–LincolnFollow
Jie Zhong, University of Nebraska–LincolnFollow
Joseph S. Francisco, University of Nebraska-LincolnFollow
Xiao Cheng Zeng, University of Nebraska-LincolnFollow

Date of this Version

2017

Citation

Chem. Sci., 2017, 8, 5385

DOI: 10.1039/c7sc01797a

Comments

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Abstract

We carry out Born–Oppenheimer molecular dynamic simulations to show that the reaction between the smallest Criegee intermediate, CH₂OO, and hydrogen sulfide (H₂S) at the air/water interface can be observed within few picoseconds. The reaction follows both concerted and stepwise mechanisms with former being the dominant reaction pathway. The concerted reaction proceeds with or without the involvement of one or two nearby water molecules. An important implication of the simulation results is that the Criegee-H₂S reaction can provide a novel non-photochemical pathway for the formation of a C–S linkage in clouds and could be a new oxidation pathway for H₂S in terrestrial, geothermal and volcanic regions.