Electronic factors in cation-anion recombinations

Sebastião J. Formosinho; Luís G. Arnaut

doi:10.1016/S0166-1280(96)04632-5

Electronic factors in cation-anion recombinations

Sebastião J. Formosinho^*, Luís G. Arnaut

^*Corresponding author for this work

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

3 Citations (Scopus)

Abstract

The intersecting-state model (ISM) anticipates the non-free-energy relationship of Ritchie for cation-anion recombination reactions when the force constants for reactants are considerably lower than those for products. This asymmetry of the potential energy curves implies that the quadratic equation of Marcus for the dependence between ΔG‡ and ΔG⁰ is not adequate for the study of such reactions. ISM was applied to the study of several recombination processes in different solvents and a linear correlation was found between the values of the electronic parameter of the model (transition state bond order, n‡), and the empirical nucleophilic parameters (N₊) of Ritchie. The role of the increase of n‡ in the α-effect of nucleophilic reactions is briefly discussed.

Original language	English
Pages (from-to)	133-141
Number of pages	9
Journal	Journal of Molecular Structure: THEOCHEM
Volume	371
Issue number	1-3 SPEC. ISS.
DOIs	https://doi.org/10.1016/S0166-1280(96)04632-5
Publication status	Published - 18 Nov 1996

Keywords

α-Effect
Cation-anion recombination
Intersecting-state model
Nucleophilic parameters

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10.1016/S0166-1280(96)04632-5

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abstract = "The intersecting-state model (ISM) anticipates the non-free-energy relationship of Ritchie for cation-anion recombination reactions when the force constants for reactants are considerably lower than those for products. This asymmetry of the potential energy curves implies that the quadratic equation of Marcus for the dependence between ΔG‡ and ΔG0 is not adequate for the study of such reactions. ISM was applied to the study of several recombination processes in different solvents and a linear correlation was found between the values of the electronic parameter of the model (transition state bond order, n‡), and the empirical nucleophilic parameters (N+) of Ritchie. The role of the increase of n‡ in the α-effect of nucleophilic reactions is briefly discussed.",

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T1 - Electronic factors in cation-anion recombinations

AU - Formosinho, Sebastião J.

AU - Arnaut, Luís G.

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AB - The intersecting-state model (ISM) anticipates the non-free-energy relationship of Ritchie for cation-anion recombination reactions when the force constants for reactants are considerably lower than those for products. This asymmetry of the potential energy curves implies that the quadratic equation of Marcus for the dependence between ΔG‡ and ΔG0 is not adequate for the study of such reactions. ISM was applied to the study of several recombination processes in different solvents and a linear correlation was found between the values of the electronic parameter of the model (transition state bond order, n‡), and the empirical nucleophilic parameters (N+) of Ritchie. The role of the increase of n‡ in the α-effect of nucleophilic reactions is briefly discussed.

KW - α-Effect

KW - Cation-anion recombination

KW - Intersecting-state model

KW - Nucleophilic parameters

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Electronic factors in cation-anion recombinations

Abstract

Keywords

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