文献类型：期刊文献

英文题名：A theoretical perspective on the structure and thermodynamics of secondary organic aerosols from toluene: molecular hierarchical synergistic effects

作者：Duan, Xianli[1];Song, Xianyu[1];Shi, Ruifang[2,3];Wang, Xuan[2,3];Chen, Suhang[1];Zhao, Shuangliang[2,3,4]

机构：[1]Chongqing Three Gorges Univ, Sch Environm & Chem Engn, Chongqing Key Lab Water Environm Evolut & Pollut, Chongqing 404020, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China;[4]Guangxi Univ, Guangxi Key Lab Petrochem Resource Proc & Proc In, Nanning 530004, Peoples R China

年份：2022

卷号：9

期号：3

起止页码：1052

外文期刊名：ENVIRONMENTAL SCIENCE-NANO

收录：;EI(收录号：20221411923166);WOS:【SCI-EXPANDED(收录号:WOS:000746915900001)】；

基金：This work was supported by the National Natural Science Foundation of China (No. 22108022, 91934302, and 21878078), the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (No. 2020Z002), the Natural Science Foundation of Chongqing (No. cstc2021jcyj-msxmX0005), and the Science and Technology Innovation Program of Wanzhou (No. wzstc20210310).

语种：英文

外文关键词：Photooxidation - Van der Waals forces - Nanoparticles - Density functional theory - Hydrogen bonds - Molecular dynamics - Probability distributions - Benzoic acid - Atmospheric chemistry - Thermodynamics

摘要：Toluene is an important constituent of liquid fuel, and it contributes to the formation of secondary organic aerosols (SOAs) under photochemical conditions. However, the underlying mechanism of toluene SOAs is not fully understood. To address this issue, an atomistic molecular dynamics (MD) approach and density functional theory (DFT) are coupled to study the molecular chemistry of toluene SOAs by examining their structural characteristics and thermodynamic properties. Both MD and DFT methods are proven to be consistent with experimental results. Our results suggest that the molecular hierarchical synergistic effects majorly determine the formation of core-shell SOA nanoparticles. In the toluene photooxidation production, pyruvic acid acts as a "bridge" that promotes concentration of benzaldehyde and benzoic acid at the surface of H2SO4-H2O clusters. Besides, the chemical composition and environmental temperature have a key role in the probability distribution and lifetime of hydrogen bonds of toluene SOAs, thus altering the formation energy barrier of gas-to-nanoparticle conversion. When compared with van der Waals interactions, electrostatic interactions are found to be the central driving force that yields stable toluene SOA nanoparticles. Our results reveal the molecular chemistry for the atmospheric aerosol and highlight the need to account for molecular hierarchical synergistic effects when assessing the atmospheric aerosol.