π-Hydrogen Bonding of Aromatics on the Surface of Aerosols: Insights from Ab Initio and Molecular Dynamics Simulation.
Molecular level insight into the interaction between volatile organic compounds (VOCs) and aerosols is crucial for improvement of atmospheric chemistry models. In this paper, the interaction between adsorbed toluene, one of the most significant VOCs in the urban atmosphere, and the aqueous surface of aerosols was studied by means of combined molecular dynamics simulations and ab initio quantum chemistry calculations. It is revealed that toluene can be stably adsorbed on the surface of aqueous droplets via hydroxyl-π hydrogen bonding between the H atoms of the water molecules and the C atoms in the aromatic ring. Further, significant modifications on the electrostatic potential map and frontier molecular orbital are induced by the solvation effect of surface water molecules, which would affect the reactivity and pathway of the atmospheric photooxidation of toluene. This study demonstrates that the surface interactions should be taken into consideration in the atmospheric chemical models on oxidation of aromatics.
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Opttics & Fine Mechanics, Chinese Academy of Sciences , Hefei, Anhui 230031, China.
Ya-Juan
YJ
Feng
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Opttics & Fine Mechanics, Chinese Academy of Sciences , Hefei, Anhui 230031, China.
Teng
T
Huang
Key Laboratory of Neutronics and Radiation Safety, Institute of Nuclear Energy Safety Technology, Chinese Academy of Sciences , Hefei, Anhui 230031, China.
Chao
C
Wang
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Opttics & Fine Mechanics, Chinese Academy of Sciences , Hefei, Anhui 230031, China.
Yi-Rong
YR
Liu
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Opttics & Fine Mechanics, Chinese Academy of Sciences , Hefei, Anhui 230031, China.
Shuai
S
Jiang
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Opttics & Fine Mechanics, Chinese Academy of Sciences , Hefei, Anhui 230031, China.
Shou-Kui
SK
Miao
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Opttics & Fine Mechanics, Chinese Academy of Sciences , Hefei, Anhui 230031, China.
Jiao
J
Chen
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Opttics & Fine Mechanics, Chinese Academy of Sciences , Hefei, Anhui 230031, China.|School of Environmental Science & Optoelectronic Technology, University of Science and Technology of China , Hefei, Anhui 230026, China.|CAS Center for Excellence in Urban Atmospheric Environment , Xiamen, Fujian 361021, China.
Wei
W
Huang