Date Published:

MAR 13

Abstract:

A Huckel-type effective Hamiltonian is used to examine the conditions for site-selected reactivity. The example is the dissociation of a positive ion, as in mass spectrometry. Coupling to the dissociative channels is included by a rate operator. We examine the time evolution of the charge and bond order matrices and of the yield of fragments following a localized initial ionization. Dissociation is found to follow the (positive) charge. Variations in the local properties can markedly change the dissociation pattern. A more statistical limit is reached when the migration of charge is unimpeded. (C) 1998 Elsevier Science B.V.