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. Graphical Abstract.
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