Nitric Acid Dissociation at an Aqueous Surface: Occurrence and Mechanism

Abstract

AbstractHere we briefly review some highlights of our recent work on the acid dissociation of nitric acid HNO3 at an aqueous surface, a proton transfer reaction of interest not only from a fundamental perspective, but also in connection with heterogeneous chemistry in a wide range of atmospheric contexts. Two types of studies of the potential acid dissociation are discussed, quantum chemical reaction path calculations to assess the reaction free energy and Car‐Parrinello molecular dynamics simulations to assess the reaction feasibility. We discuss the agreement and disagreement between the predictions of these two calculations as a function of the initial location of the HNO3 molecule, ranging from a positioning on top of the aqueous surface to one several water layers below the surface. Special attention is given to the four key water solvent motions found to be necessary for the proton transfer reaction to occur. Finally, an Eigen cation, rather than a Zundel cation, is in all cases found to be predominant next to the nitrate ion in contact ion pairs produced in the acid dissociation. This predominance remains, although diminished, for solvent‐separated ion pairs.