Environment Research Institute, Shandong University, Qingdao 266237, China; State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Science, Beijing 100012, China.
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Science, Beijing 100012, China.
J Environ Sci (China). 2020 Sep;95:130-140. doi: 10.1016/j.jes.2020.03.033. Epub 2020 May 8.
Interactions of the three common atmospheric bases, dimethylamine ((CH)NH), methylamine (CHNH), ammonia (NH), all considered to be efficient stabilizers of binary clusters in the Earth's atmosphere, with HSO, the key atmospheric precursor, and 14 common atmospheric organic acids (COAs) (formic, acetic, oxalic, malonic, succinic, glutaric acid, adipic, benzoic, phenylacetic, pyruvic, maleic acid, malic, tartaric and pinonic acids) have been studied using the density functional theory (DFT) and composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA)(HSO), (COA)(B1), (COA)(B2) and (COA)(B3) dimers and (COA)(HSO)(B1), (COA)(HSO)(B2) and (COA)(HSO)(B3) trimers, where B1, B2 and B3 refer to (CH)NH, CHNH and NH, respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing HSO have been studied. Our investigation shows that interactions of HSO with COA, (CH)NH, CHNH and NH lead to the formation of more stable mixed dimers and trimers than (HSO) and (HSO)(base), respectively, and emphasize the importance of common organic species for early stages of atmospheric nucleation. We also show that although amines are generally confirmed to be more active than NH as stabilizers of binary clusters, in some cases mixed trimers containing NH are more stable thermodynamically than those containing CHNH. This study indicates an important role of COA, which coexist and interact with that HSO and common atmospheric bases in the Earth atmosphere, in formation of stable pre-nucleation clusters and suggests that the impacts of COA on new particle formation (NPF) should be studied in further details.
已使用密度泛函理论 (DFT) 和组合高精度 G3MP2 方法研究了三种常见大气碱基（二甲胺 ((CH)NH)、甲胺 (CHNH)和氨 (NH)）与大气前体 HSO 和 14 种常见大气有机酸 (COA)（甲酸、乙酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、苯甲酸、苯乙酸、丙酮酸、马来酸、苹果酸、酒石酸和 pinonic 酸）的相互作用。研究了混合 (COA)(HSO)、(COA)(B1)、(COA)(B2) 和 (COA)(B3) 二聚体以及 (COA)(HSO)(B1)、(COA)(HSO)(B2) 和 (COA)(HSO)(B3) 三聚体的热力学稳定性，其中 B1、B2 和 B3 分别指 (CH)NH、CHNH 和 NH。研究了它们对含有 HSO 的团簇热力学稳定性的影响。我们的研究表明，HSO 与 COA、(CH)NH、CHNH 和 NH 的相互作用导致形成的混合二聚体和三聚体比 (HSO) 和 (HSO)(碱基) 分别更稳定，并强调了常见有机物种对大气成核早期阶段的重要性。我们还表明，尽管胺通常被证实为二元团簇稳定化更活跃的物质，但在某些情况下，含有 NH 的混合三聚体在热力学上比含有 CHNH 的三聚体更稳定。这项研究表明了 COA 的重要作用，COA 与 HSO 和常见大气碱基共存并相互作用，在稳定的成核前团簇形成中起作用，并表明应进一步详细研究 COA 对新粒子形成 (NPF) 的影响。
