Exploration of the atmospheric reactivity of N2O5 and HCl in small water clusters using electronic structure methods

Exploration of the reactivity of N2O5 with two Si(OH)4 monomers using electronic structure methods

“…[17] The reaction energy using the same method is also in agreement with the previous ab initio calculations with larger basis sets, BLYP/6-311þþG(d,p) and MP2/6-311þþG(3df,3pd). [16,19] In this case (MP2//B3LYP þ TC) showed to be more accurate than the B3LYP functional. 2 .…”

“…[7,11,13] The second step can be compared to the gas phase hydrolysis of an isolated N 2 O 5 with one water molecule studied by Hillier and coworkers. [16] The mechanism of the first step, which is an oxolation mechanism, is the reverse reaction of the hydrolysis of H 6 Si 2 O 7 studied by Hillier and coworkers. [11] The examination of the imaginary mode of TSa1 shows that the nucleophilic attack of one hydroxo ligand O(3)H(2) to the nearest Si(1) center, induces a migration of ).…”

“…[c] Rodriguez-Fortea et al [19] and McNamara et al [16] The value for the free energy corresponds to 180 K.…”

“…In the second step, the hydrolysis of N 2 O 5 is similar to the identified pathway of Hillier and coworkers. [16] The reaction proceeds via nucleophilic attack of water at N(2), reacting via a six-membered ring transition state where the transferring proton of the water H(1) approaches O(2) of the forming nitrate in the transition state (TS1). The breaking N(1)AO…N(2) bond has lengthened to 2.20 Å and the forming N(2)…O(1) bond of nitric acid has shortened to 1.97 Å .…”

“…[4,14] Aside from experimental investigations, there are also some theoretical studies dealing with the reaction of N 2 O 5 . [15][16][17][18][19] Little is known about the detailed mechanisms that occur in the process and the possible role of the hydroxyl groups on the silica surface. The two Si(OH) 4 monomers are simple models to study the N 2 O 5 interaction with two hydroxyl groups on different Si atoms.…”