Quantum chemical study of the structure, spectroscopy and reactivity of NO + .(H 2 O) n =1−5 clusters

Abstract

Quantum chemical methods including Møller–Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO + .(H 2 O) n =1−5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange–correlation functionals with a low fraction of Hartree–Fock exchange give a binding energy of NO + .(H 2 O) that is too high and incorrectly predict the lowest energy structure of NO + .(H 2 O) 2 , and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO + . Ab initio molecular dynamics (AIMD) simulations were performed to study the NO + .(H 2 O) 5 H + .(H 2 O) 4 + HONO reaction to investigate the formation of HONO from NO + .(H 2 O) 5 . Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO + .(H 2 O) 5 complex following its formation. This article is part of the theme issue ‘Modern theoretical chemistry’.