TY - JOUR
T1 - Charge directed reactivity
T2 - A simple electronic model, exhibiting site selectivity, for the dissociation of ions
AU - Remacle, F.
AU - Levine, R. D.
AU - Ratner, M. A.
N1 - Funding Information:
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.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 1998/3/13
Y1 - 1998/3/13
N2 - 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.
AB - 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.
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U2 - 10.1016/S0009-2614(97)01314-6
DO - 10.1016/S0009-2614(97)01314-6
M3 - Article
AN - SCOPUS:0032512962
VL - 285
SP - 25
EP - 33
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 1-2
ER -