The effect of (H2O)n (n=1-3) clusters on the reaction of HONO with HCl: a mechanistic and kinetic study

The reaction between HONO and HCl is a possible pathway for the generation of ClNO, which is prone to photolyze, produce chlorine radicals, and accelerate the oxidation of tropospheric VOCs. Current experimental and theoretical studies have significant differences in rate constants under similar conditions. This study aims to examine the reasons for this difference. In this study, the effects of a single water molecule, water dimer, water trimer, excess HCl and excess HONO on the reaction mechanism of HONO + HCl were studied at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(2df,2p) level and the rate constants of each reaction channel were calculated. Our results showed that the reaction potential barrier of HONO with HCl was the lowest only when the water dimer was present, and the reaction rate constants were close to the experimental results, and both the cis-HONOMIDLINE HORIZONTAL ELLIPSIS(H2O)(2) + HCl and the trans-HONOMIDLINE HORIZONTAL ELLIPSIS(H2O)(2) + HCl reaction paths are likely to occur. We think that the reason for the inconsistency between experimental and theoretical results is that the water dimer is involved in the reaction in experiments.