ABSTRACT A comprehensive investigation of the roles of water catalysts on O3 with HNO in the troposphere has been carried out by quantum chemical calculations at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311++G(2d,2p) levels of theory. Besides, the AIMD (ab initio Molecular Dynamics) simulation also used to help us to understand the mechanism of this reaction. The results show that the HNO + O3 reaction undergoes a channel for the formation of NO + HO3 and overcomes the energy barrier of 1.60 kcal·mol−1. After adding water molecules, the obtained product did not change, but the potential energy surface was much more complicated than the bare reaction, and it went through four reaction channels of HNO···H2O + O3, H2O···HNO + O3, H2O···O3 + HNO and O3···H2O + HNO. Among them, the channel HNO···H2O + O3 is the dominant channel for water molecules to participate in the reaction. Overall, these results show how water catalyzed the gas-phase reactions under atmospheric conditions.

中文翻译：

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水对对流层条件下 HNO + O3 反应生成 HO3 + NO 的催化作用

摘要 通过量子化学计算，CCSD(T)/aug-cc-pVTZ//M06-2X/6-311++G( 2d,2p) 理论水平。此外，AIMD（ab initio Molecular Dynamics）模拟也有助于我们理解该反应的机理。结果表明，HNO + O3 反应经历了形成 NO + HO3 的通道并克服了 1.60 kcal·mol-1 的能垒。加入水分子后，所得产物没有变化，但势能面比裸反应复杂得多，经过HNO…H2O+O3、H2O…HNO+O3四个反应通道， H2O…O3 + HNO 和 O3…H2O + HNO。他们之中，通道HNO…H2O + O3 是水分子参与反应的主要通道。总体而言，这些结果显示了水如何在大气条件下催化气相反应。