Mechanisms and competition of halide substitution and hydrolysis in reactions of N(2)O(5) with seawater

S(N)2-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 N(2)O(5) and seawater. N(2)O(5) plays a major role in regulating levels of O(3), OH, NO(x), and CH(4). While the reactions of N(2)O(5) 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 ClNO(2), which occurs despite the fact that hydrolysis (to HNO(3)) is energetically more favorable. We determine key features of the reaction landscape that account for this behavior in a theoretical study of the cluster N(2)O(5)/Cl(−)/H(2)O. This was carried out using ab initio molecular dynamics to determine reaction pathways, structures, and time scales. While hydrolysis of N(2)O(5) occurs in the absence of Cl(−), results here reveal that a low-lying pathway featuring halide substitution intermediates enhances hydrolysis.