Charge directed reactivity: A simple electronic model, exhibiting site selectivity, for the dissociation of ions

F. Remacle; R. D. Levine; M. A. Ratner

doi:10.1016/S0009-2614(97)01314-6

Charge directed reactivity: A simple electronic model, exhibiting site selectivity, for the dissociation of ions

F. Remacle, R. D. Levine^*, M. A. Ratner

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

81 Scopus citations

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)
Pages (from-to)	25-33
Number of pages	9
Journal	Chemical Physics Letters
Volume	285
Issue number	1-2
DOIs	https://doi.org/10.1016/S0009-2614(97)01314-6
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

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10.1016/S0009-2614(97)01314-6

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title = "Charge directed reactivity: A simple electronic model, exhibiting site selectivity, for the dissociation of ions",

abstract = "A H{\"u}ckel-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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note = "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.",

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T2 - A simple electronic model, exhibiting site selectivity, for the dissociation of ions

AU - Remacle, F.

AU - Levine, R. D.

AU - Ratner, M. A.

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PY - 1998/3/13

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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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Charge directed reactivity: A simple electronic model, exhibiting site selectivity, for the dissociation of ions

Abstract

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