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A single water molecule accelerating the atmospheric reaction of HONO with ClO

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Abstract

The role of a single water molecule on the atmospheric reaction of HONO + ClO is systematically investigated employing quantum chemical calculation combined with harmonic transition state theory. Two reaction pathways, cis-HONO + ClO and trans-HONO + ClO, are identified for the naked reaction, which depends on the configurations of HONO. When adding a single water molecule to this reaction, the rate constants of cis-HONO + ClO and trans-HONO + ClO pathways are 7.97 × 10−21 and 2.29 × 10−17 cm3 molecule−1 s−1, respectively, larger than the corresponding naked reaction. To further understand the role of water on the HONO + ClO reaction, it is necessary to calculate the effective rate constant by considering the concentration of water. It shows that the effective rate constants of water-assisted cis-HONO + ClO pathway are much smaller than those of the naked reaction, whereas the presence of water accelerates the trans-HONO + ClO at room temperature. This study demonstrates that water has a positive role in the pathway of trans-HONO + ClO by modifying the stabilities of reactant complexes and transition states through the hydrogen bond formation, which contributes to the sink of atmospheric HONO. In addition, the kinetic branching ratio indicates that the favorable reaction is the trans-HONO + ClO instead of the cis-HONO + ClO pathway, in contrast to the naked reaction. These results reveal the importance of water in the evaluation of the fate of active species in the atmosphere.

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Funding

This work was supported by National Natural Science Foundation of China (21577080, 91644214), Shandong Natural Science Fund for Distinguished Young Scholars (JQ201705), Shandong Key R&D Program (2018GSF117040), and Fundamental Research Funds of Shandong University (2017JQ01). The scientific calculations in this paper have been done on the HPC Cloud Platform of Shandong University.

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  1. Environment Research Institute, Shandong University, Binhai Road 72, Qingdao, 266237, China

    Shanshan Tang & Lin Du

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  1. Shanshan Tang
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  2. Lin Du
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Correspondence to Lin Du.

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Tang, S., Du, L. A single water molecule accelerating the atmospheric reaction of HONO with ClO. Environ Sci Pollut Res 26, 27842–27853 (2019). https://doi.org/10.1007/s11356-019-05999-x

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