Nitrite ion formation: Nonempirical simulation in terms of cluster model

Abstract

AbstractNeutral 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 6‐31++G** 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. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004