Nitrite ion formation: Nonempirical simulation in terms of cluster model

Abstract

Neutral and negatively charged nitrogen dioxide molecule either individual or involved in a complex cluster with up to 50 water molecules is nonempirically simulated in the second order of the Møller-Plesset perturbation theory with the unrestricted Hartree-Fock function with the use of atomic basis functions of the 6-31ϩϩG** set and effective fragment potentials for a part of water molecules. The structures corresponding to the local minima of the potential energy surfaces of neutral and anionic clusters are considered, and their dissociation energies are estimated. The geometric parameters of the cavities formed around nitrogen dioxide and its anion in the H-bond network of water clusters are compared. The vertical electron detachment energies of the anions and the electron affinities of the parent neutral complex clusters depending on the number of water molecules involved are used for estimating the corresponding energetic characteristics of infinitely diluted aqueous nitrogen dioxide systems.

Nitrogen dioxide at the air–water interface: trapping, absorption, and solvation in the bulk and at the surface

“…There are a small number of ab initio studies of the weakly-bound NO 2 (X ˜2A 1 )-H 2 O complex, either in the gas phase or solvated with additional water molecules. [44][45][46] The global minimum has been found to be a non-hydrogen-bonded C s structure, with the nitrogen of NO 2 closest to the oxygen of water. 45,46 The C s structure of ref.…”

“…[44][45][46] The global minimum has been found to be a non-hydrogen-bonded C s structure, with the nitrogen of NO 2 closest to the oxygen of water. 45,46 The C s structure of ref. 44 which found the oxygens of NO 2 to be closer to the hydrogens of water is likely due to the use of a basis set that was too small.…”

Efficient Conversion of Nitrogen Dioxide into Nitrous Acid on Ice Surfaces

“…Kinetic studies − have shown that the rate of NO 2 hydrolysis is accelerated in the presence of liquid water films, but the detailed mechanism of the heterogeneous hydrolysis is not clearly understood. Theoretical studies have examined the effect of water solvation on the reaction , and calculated the energetic stability of the water complexes of NO 2 and nitrous acid . These studies indicate that the presence of multiple (up to three) water molecules does not significantly reduce the energy barrier of the hydrolysis compared to nonsolvation.…”