Quantum chemical insights into the dissociation of nitric acid on the surface of aqueous electrolytes

摘要

Recent experiments in our laboratory have shown that the probability of gaseous HNO3 deprotonation on the surface of water is dramatically enhanced by anions. Herein, we report a quantum chemical study of how a HNO _3 molecule transfers its proton upon approaching water clusters containing or not a chloride ion. We find that HNO3 always binds to the outermost water molecules both via donating and accepting hydrogen-bonds, but the free energy barrier for subsequent proton transfer into the clusters is greatly reduced in the presence of Cl~-. As the dissociation of HNO_3 embedded in water clusters is barrierless, we infer that interfacial proton transfer to water is hindered by the cost of creating a cavity for NO_3 ~-. Our findings suggest that nearby anions catalyze HNO_3 dissociation by preorganizing interfacial water and drawing the proton - away from the incipient [H~+ - -NO _3 ~-] close ion-pairs generated at the interface. This catalytic mechanism would operate in the 1 mM Cl~- range (1 Cl ~- in ～5.5 × 10~4 water molecules) covered by our experiments if weakly adsorbed HNO_3 were able to explore extended surface domains before desorbing or diffusing (undissociated) into bulk water.