Nitryl chloride (ClNO2) and nitrosyl chloride (ClNO) are potential sources of highly reactive atmospheric chlorine atoms, hence of much interest, but their formation pathways are unknown. This work predicts production of these nitrogen oxychlorides from ab initio molecular dynamics (AIMD) simulations of N2O5 or an NO2 dimer on the surface of a thin film of water which is struck by gaseous HCl. Both of these heterogeneous reactions proceed at the liquid/vapor interface by an SN2 mechanism where the nucleophile is chloride ion formed from the ionization of HCl on the aqueous surface. The film of water enhances the otherwise very slow gas phase reaction to occur by (1) stabilizing and localizing the adsorbed N2O5 or NO2 dimer so it is physically accessible for reaction, (2) ionizing the impinging HCl, and (3) activating the adsorbed oxide for nucleophilic attack by chloride. Though both nitrogen oxychloride products are produced by SN2 reactions, the N2O5 mechanism is unusual in that the electrophilic N atom to be attacked oscillates between the two normally equivalent NO2 groups. Chloride ion is found to react with N2O5 less efficiently than with N2O4. The simulations provide an explanation for this. These substitution/elimination mechanisms are new for NOx/y chemistry on thin water films and cannot be derived from small cluster models.

Ab initio molecular dynamics simulations of the liquid–vapor interface are presented for thin slabs of 72 water molecules containing a single molecule of sulfuric acid. Trajectories in the 306–330 K range are calculated for two functionals with double- and triple-ζ quality basis sets. Comparisons are made between BLYP and HCTH/120 results for the slab simulations and for bulk simulations of one H2SO4 in a periodic box with 63 waters. Good agreement is found with the available experimental data and the results of other relevant AIMD studies with respect to ionization of the acid, size of the coordination shells, partitioning of the ions with the hydronium exhibiting a surface preference and the anions in the interior, and the orientational distributions for the hydronium ions and for the surface/subsurface water molecules. The major differences in the performance of the two functionals are attributable to the greater basicity of the anion oxygen atoms with the HCTH functional and the more structured aqueous solution with BLYP. The enhanced basicity results in larger aqueous coordination shells for the anion oxygens. The structuring of the BLYP aqueous solution is observed in the corrugation of the water density profile, the higher first peak in gOO(r), and a smaller water self-diffusion constant. This structuring with the BLYP functional yields anion hydrogen bonds that endure longer and where the dissociated ions more rapidly and directly segregate in the slab. The simulations indicate that aqueous surfaces containing ionizable diprotic acids can be modeled with rather modest sized systems and be informative.

Chlorine atoms are highly reactive free radicals known to catalyze ozone depletion in the stratosphere and organic oxidation in the troposphere. They are readily produced photolytically upon irradiation of some stable Cl containing species, for instance, nitrosyl chloride, ClNO. We predict the formation of ClNO using ab initio molecular dynamics (AIMD) simulations of an NO2 dimer on the surface of a thin film of water upon which gaseous HCl impinges. The reactant is chloride ion formed when HCl ionizes on the water film. The same mechanism for ClNO production may occur in humid environments when ONONO2 (the asymmetric NO2 dimer examined here) comes in contact with either HCl or sea salt. The film of water serves to (1) stabilize ONONO2 on the film surface so that it is localized and physically accessible for reaction, (2) provide the medium to ionize HCl, and (3) activate ONONO2 making it more susceptible to nucleophilic attack by chloride. This substitution/elimination mechanism is new for NOx chemistry on thin water films and could not be derived from studies on small clusters.Keywords: ab initio molecular dynamics; AIMD; lower atmosphere;

Nitryl chloride (ClNO2) and nitrosyl chloride (ClNO) are potential sources of highly reactive atmospheric chlorine atoms, hence of much interest, but their formation pathways are unknown. This work predicts production of these nitrogen oxychlorides from ab initio molecular dynamics (AIMD) simulations of N2O5 or an NO2 dimer on the surface of a thin film of water which is struck by gaseous HCl. Both of these heterogeneous reactions proceed at the liquid/vapor interface by an SN2 mechanism where the nucleophile is chloride ion formed from the ionization of HCl on the aqueous surface. The film of water enhances the otherwise very slow gas phase reaction to occur by (1) stabilizing and localizing the adsorbed N2O5 or NO2 dimer so it is physically accessible for reaction, (2) ionizing the impinging HCl, and (3) activating the adsorbed oxide for nucleophilic attack by chloride. Though both nitrogen oxychloride products are produced by SN2 reactions, the N2O5 mechanism is unusual in that the electrophilic N atom to be attacked oscillates between the two normally equivalent NO2 groups. Chloride ion is found to react with N2O5 less efficiently than with N2O4. The simulations provide an explanation for this. These substitution/elimination mechanisms are new for NOx/y chemistry on thin water films and cannot be derived from small cluster models.