Abstract
A Hückel-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.
Original language | English (US) |
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Pages (from-to) | 25-33 |
Number of pages | 9 |
Journal | Chemical Physics Letters |
Volume | 285 |
Issue number | 1-2 |
DOIs | |
State | Published - Mar 13 1998 |
Funding
We thank R. Weinkauf and E.W. Schlag for discussions. This work was supported by the Volkswagen Foundation. Computational facilities were also provided by SFB 377. MAR thanks the MURI program of DoD for support.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry