UC Irvine

S_N2-type halide substitution and hydrolysis are two of the most ubiquitous reactions in chemistry. The interplay between these processes is fundamental in atmospheric chemistry through reactions of N₂O₅ and seawater. N₂O₅ plays a major role in regulating levels of O₃, OH, NO _x , and CH₄. While the reactions of N₂O₅ and seawater are of central importance, little is known about their mechanisms. Of interest is the activation of Cl in seawater by the formation of gaseous ClNO₂, which occurs despite the fact that hydrolysis (to HNO₃) is energetically more favorable. We determine key features of the reaction landscape that account for this behavior in a theoretical study of the cluster N₂O₅/Cl^-/H₂O. This was carried out using ab initio molecular dynamics to determine reaction pathways, structures, and time scales. While hydrolysis of N₂O₅ occurs in the absence of Cl^-, results here reveal that a low-lying pathway featuring halide substitution intermediates enhances hydrolysis.