Modeling of substituent effects: self-parametrization, a case of interdependence of the coefficients, illustrated on the linear plus cross-term models - Archive ouverte HAL
Article Dans Une Revue Journal of Mathematical Chemistry Année : 2001

Modeling of substituent effects: self-parametrization, a case of interdependence of the coefficients, illustrated on the linear plus cross-term models

B Blaive
  • Fonction : Auteur
J Ziegler

Résumé

The effect of one or several substituents X-i on a molecular property f (reaction rate, spectroscopic property, etc.) is often described in terms of substituent parameters lambda(i) (X) depending on the nature X of the substituent, and the position i of substitution. We call self-parametrization the case when the substituents are parameterized by the value lambda(i) (X) = f(i) (X) of f itself in the molecule monosubstituted by X in position i. On the example of the linear plus cross-term models, we show that self-parametrization implies that the coefficients of the model are interdependent. The theoretical relations between them are given, for equivalent or nonequivalent positions of substitution, and tested on measured acid-base equilibrium constants, and NMR coupling constants.

Domaines

Psychologie

Dates et versions

hal-01441421 , version 1 (19-01-2017)

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Citer

B Blaive, J Ziegler. Modeling of substituent effects: self-parametrization, a case of interdependence of the coefficients, illustrated on the linear plus cross-term models. Journal of Mathematical Chemistry, 2001, 30 (1), pp.69-81. ⟨10.1023/A:1013105427633⟩. ⟨hal-01441421⟩

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