Noncovalent Interactions in Hydrated Nitrosonium Ion Clusters Mediated by Hydrogen-Bonded Water Networks.

Abstract

As important species in the D region of the ionosphere, hydrated nitrosonium ion clusters [NO+(H2O)n] are also archetypal and concise models to illustrate effects of different solvent shells. We have investigated noncovalent interactions in NO+(H2O)3 and NO+(H2O)4 isomers with high levels of ab initio and symmetry-adapted perturbation theory (SAPT) methods. On the basis of our computations, the exchange energies become much more repulsive, whereas the induction energies are significantly more attractive for the noncovalent interactions of NO+ with hydrogen-bonded water chains. Combined with analyses of the electron densities for the NO+(H2O)3 and NO+(H2O)4 isomers, we propose that the counteracting effect of the exchange and induction energies could be deemed as an index for the tendency to form the HO-NO covalent bond. Moreover, we have also found that the third-order induction terms are very important to evaluate reasonable charge transfer energies with the SAPT computations.