Barrierless HNO3 formation from the hydrolysis reaction of NO2 with Cl atom in the atmosphere
Barrierless HNO3 formation from the hydrolysis reaction of NO2 with Cl atom in the atmosphere
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NO2 与大气中的 Cl 原子发生水解反应，无阻碍地形成 HNO3
DOI：
10.1016/j.atmosenv.2021.118871
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发表时间：
2021-11
影响因子：
5
通讯作者：
Xianwei Zhao
中科院分区：
文献类型：
--
作者：
Xianwei Zhao
硝酸（HNO 3）是大气中的主要污染物之一，对大气污染有重要影响。然而，对于HNO 3在海洋边界层中的形成途径，目前还知之甚少.在这里，我们显示的证据HNO 3形成的氯（Cl）自由基和二氧化氮（NO2），1-3水分子，以及在空气-水界面上，基于直接Born-Oppenheimer分子动力学（BOMD）模拟。使用热力学积分计算了（Cl）（NO 2）（H 2 O）1（一水合物）系统沿反应坐标的相对自由能变化沿着，表明一水合物系统没有自由能垒，为26.5 kcal mol −1放能。这表明从一水合物体系中生成HNO 3是有利的.对于所研究的所有系统，使用BOMD模拟直接观察到HNO 3的形成，并且只有一个水分子参与反应。然而，环结构，这是预计将普遍存在于空气-水界面上，没有观察到。研究表明，在MBL区，Cl原子、NO2和水分子的反应对HNO 3的生成起着重要作用。·研究了海洋边界层（MBL）中HNO 3的形成。·一水合物体系没有表现出自由能垒，是放热的26.5 kcal mol −1。·只有一个水分子直接参与HNO 3的形成。
Nitric acid (HNO 3 ) is one of the main pollutants in the atmosphere and has an important effect on the air pollution. However, the formation pathways of HNO 3 are still poorly understood in the marine boundary layer (MBL). Here, we show evidence of the formation of HNO 3 from chlorine (Cl) radical and nitrogen dioxide (NO 2 ), with 1–3 water molecules, as well as on the air-water interface, based on the direct Born-Oppenheimer molecular dynamics (BOMD) simulation. The relative free energy change along the reaction coordinates for the (Cl)(NO 2 )(H 2 O) 1 (monohydrate) system was calculated using thermodynamic integration, revealing that the monohydrate system exhibited no free energy barrier and was 26.5 kcal mol −1 exergonic. This suggests that the formation of HNO 3 from the monohydrate system is thermodynamically favorable. For all the systems studied, the formation of HNO 3 was directly observed using BOMD simulations, and only one water molecule participates in the reaction. However, loop structures, which were expected to be ubiquitous on the air-water interface, were not observed. This study identifies the importance of the reactions of Cl atom, NO 2 , and water molecules in the formation of HNO 3 in the MBL region. • The formation of HNO 3 in the marine boundary layer (MBL) were investigated. • The monohydrate system exhibited no free energy barrier and was exergonic 26.5 kcal mol −1 . • Only one water molecule is directly involved in the formation of HNO 3 .
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影响因子：
11.4
作者：
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64.8
作者：
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通讯作者：
Brown, Steven S.
DOI：
10.1073/pnas.1807719115
发表时间：
2018-06
期刊：
Proceedings of the National Academy of Sciences
影响因子：
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作者：
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通讯作者：
Lei Li;Z. Duan;Hui Li;Chongqin Zhu;G. Henkelman;J. S. Francisco;X. Zeng
影响因子：
15
作者：
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通讯作者：
Zeng, Xiao Cheng