Theoretical study of atmospheric clusters: HNO3–HCl–H2O

Abstract

Nitric acid, hydrochloric acid and water can form stable aggregates with atmospheric implications, for instance at the surface of polar stratospheric clouds. The structure, stability and chemical properties of these ternary complexes are studied by means of high level theoretical calculations (hybrid DFT B3LYP method along with aug-cc-pVQZ basis set). From the many possible systems that these molecules could form, only 15 are found to yield stable structures, well characterized by a minimum in their potential energy surfaces. These aggregates are studied in detail. They can be collected in three families, according to the role played by each species in the different hydrogen bonding links that result and provide the basis for the stabilization of the clusters. Water and HCl can be H-donors to almost every O atom of HNO₃, which in turn can donate its H atom to the other two molecules. Two special cases are found, one in which H₂O plays a central role, and another with a three-dimensional structure, in contrast to the basically planar frame of the other clusters. Bonding properties are investigated for the whole series using AIM methods. The elongation of the H–Cl bond as a consequence of the aggregate creation is inspected in detail, as it may provide a clue to the lability of this molecule with implications in atmospheric processes. The Gibbs free energy calculated for these clusters shows that some of them could form spontaneously in the range of temperatures of the stratosphere.