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.
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.
UR - http://www.scopus.com/inward/record.url?scp=0032512962&partnerID=8YFLogxK
U2 - 10.1016/S0009-2614(97)01314-6
DO - 10.1016/S0009-2614(97)01314-6
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AN - SCOPUS:0032512962
SN - 0009-2614
VL - 285
SP - 25
EP - 33
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-2
ER -