A density functional study of H2O-OClO, (H2O)(2)-OClO and H2O-ClOO complexes

We have calculated the minimum structures for the complexes of chlorine dio xide with water. We have also computed vibrational and rotational frequenci es, as well as binding energies for these complexes. H2O-OClO, in which an oxygen atom of OClO is bonded to a hydrogen of H2O, has a binding energy of 2.0 kcal mol(-1) at the highest level of theory. H2O-ClOO, which is bonded through the chlorine of ClOO and a hydrogen of water, has a binding energy of 1.3 kcal mol(-1). We also studied the complex of two waters bound to th e OClO molecule in order to explain the reactivity of this molecule in the aqueous phase. (C) 2000 Elsevier Science B.V. All rights reserved.