Theoretical study of stratospheric relevant anions: nitrate-nitric acid complexes

The ion complexes NO3-(HNO3)n, n = 1-3, have been studied by means of ab initio calculations at the B3LYP/aug-cc-pVTZ level of theory. These systems are the most abundant anionic clusters below approximately 30 km altitude in the stratosphere and also in the upper troposphere. These complexes display short strong hydrogen bonds, which should be considered to explain their abundance in the atmosphere. Equilibrium geometries, harmonic frequencies, relative energies, and thermochemical data have been calculated for these anions for the first time. The calculations indicate small differences of energy in the variation of the two nitrate groups from planarity to an almost perpendicular form for n = 1. Planar geometries are found for n = 2 and 3 to give rise to a highly symmetric C(3h) NO3-(HNO3)3. In all the cases, binding energies close to those of covalent compounds are estimated. When experimental data are available, good correlations are found with our results.