Reaction of Criegee Intermediate with Nitric Acid at the Air–Water Interface

• DOI: 10.1021/jacs.8b01191
• Publication Date: 2018-03-22T11:40:20Z
• Authors: Manoj Kumar; Jie Zhong; Xiao Cheng Zeng; Joseph S. Francisco
• Keywords: Nitric acid; Interface (matter)

The role of aqueous surfaces in promoting atmospheric chemistry is increasingly being recognized. However, the bimolecular chemistries Criegee intermediates, which influence tropospheric budget OH radicals, organic acids, hydroperoxides, nitrates, sulfates, and particulate material, remain less explored on an surface. Herein we have employed Born–Oppenheimer molecular dynamics simulations two-layer ONIOM (QM:MM) electronic embedding scheme to study reaction spectroscopic signal anti-CH3CHOO with nitric acid (HNO3) at air–water interface, expected be important polluted urban environments. results reveal that water surface, HNO3-mediated hydration most dominant pathway, whereas traditionally believed direct between HNO3, formation nitrooxyethyl hydroperoxide, only minor channel. Both pathways follow a stepwise mechanism interface occur picosecond time scale. These new reactions are relevant hazy environments globally regions where nitrates sulfates abundantly present. During period, high relative humidity presence fog droplets may favor over hydroperoxide forming reaction. A similar intermediates could surface for possess HNO3-like functionalities, play improving our knowledge terrestrial equatorial northern latitudes. calculations suggest N–O stretching bands around 1600–1200 cm–1 NO2 bending band 750 used as markers distinguishing it from hydrooxyethyl