Phenomenological chemical reactivity theory for mobile electrons

Mauricio Gonzalez-Suarez, Arie Aizman, Renato Contreras

Resultado de la investigación: Article

13 Citas (Scopus)

Resumen

We present herein a model to deal with the chemical reactivity, selectivity and site activation concepts of π electron systems derived by merging the classical Coulson-Longuet-Higgins response function theory based on the Hückel molecular orbital (HMO) theory and the conceptual density functional theory. HMO-like expressions for the electronic chemical potential, chemical hardness and softness, including their local counterparts, atomic and bond Fukui functions and non-local response functions are derived. It is shown that sophisticated non-local concepts as site activation may be cast into deeper physical grounds by introducing a simplified version of static response functions. In this way, useful quantities such as self and mutual polarizabilities originally defined through the HMO parameters can be redefined as self and mutual softnesses. The model is illustrated by discussing the classical Hammett free energy relationship describing inductive substituent effects on the reactivity of benzoic acids.

Idioma originalEnglish
Páginas (desde-hasta)45-54
Número de páginas10
PublicaciónTheoretical Chemistry Accounts
Volumen126
N.º1
DOI
EstadoPublished - may 2010

Huella dactilar

Chemical reactivity
Molecular orbitals
molecular orbitals
reactivity
Electrons
Chemical activation
activation
softness
electrons
Catalyst selectivity
Chemical potential
Benzoates
benzoic acid
Merging
Free energy
Density functional theory
casts
hardness
selectivity
Hardness

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

Gonzalez-Suarez, Mauricio ; Aizman, Arie ; Contreras, Renato. / Phenomenological chemical reactivity theory for mobile electrons. En: Theoretical Chemistry Accounts. 2010 ; Vol. 126, N.º 1. pp. 45-54.
@article{880c5da70f184ce9a7d4c76eafb2daee,
title = "Phenomenological chemical reactivity theory for mobile electrons",
abstract = "We present herein a model to deal with the chemical reactivity, selectivity and site activation concepts of π electron systems derived by merging the classical Coulson-Longuet-Higgins response function theory based on the H{\"u}ckel molecular orbital (HMO) theory and the conceptual density functional theory. HMO-like expressions for the electronic chemical potential, chemical hardness and softness, including their local counterparts, atomic and bond Fukui functions and non-local response functions are derived. It is shown that sophisticated non-local concepts as site activation may be cast into deeper physical grounds by introducing a simplified version of static response functions. In this way, useful quantities such as self and mutual polarizabilities originally defined through the HMO parameters can be redefined as self and mutual softnesses. The model is illustrated by discussing the classical Hammett free energy relationship describing inductive substituent effects on the reactivity of benzoic acids.",
keywords = "Phenomenological reactivity theory, Self and mutual softnesses, Semi-empirical response functions",
author = "Mauricio Gonzalez-Suarez and Arie Aizman and Renato Contreras",
year = "2010",
month = "5",
doi = "10.1007/s00214-009-0674-1",
language = "English",
volume = "126",
pages = "45--54",
journal = "Theoretical Chemistry Accounts",
issn = "1432-881X",
publisher = "Springer New York",
number = "1",

}

Phenomenological chemical reactivity theory for mobile electrons. / Gonzalez-Suarez, Mauricio; Aizman, Arie; Contreras, Renato.

En: Theoretical Chemistry Accounts, Vol. 126, N.º 1, 05.2010, p. 45-54.

Resultado de la investigación: Article

TY - JOUR

T1 - Phenomenological chemical reactivity theory for mobile electrons

AU - Gonzalez-Suarez, Mauricio

AU - Aizman, Arie

AU - Contreras, Renato

PY - 2010/5

Y1 - 2010/5

N2 - We present herein a model to deal with the chemical reactivity, selectivity and site activation concepts of π electron systems derived by merging the classical Coulson-Longuet-Higgins response function theory based on the Hückel molecular orbital (HMO) theory and the conceptual density functional theory. HMO-like expressions for the electronic chemical potential, chemical hardness and softness, including their local counterparts, atomic and bond Fukui functions and non-local response functions are derived. It is shown that sophisticated non-local concepts as site activation may be cast into deeper physical grounds by introducing a simplified version of static response functions. In this way, useful quantities such as self and mutual polarizabilities originally defined through the HMO parameters can be redefined as self and mutual softnesses. The model is illustrated by discussing the classical Hammett free energy relationship describing inductive substituent effects on the reactivity of benzoic acids.

AB - We present herein a model to deal with the chemical reactivity, selectivity and site activation concepts of π electron systems derived by merging the classical Coulson-Longuet-Higgins response function theory based on the Hückel molecular orbital (HMO) theory and the conceptual density functional theory. HMO-like expressions for the electronic chemical potential, chemical hardness and softness, including their local counterparts, atomic and bond Fukui functions and non-local response functions are derived. It is shown that sophisticated non-local concepts as site activation may be cast into deeper physical grounds by introducing a simplified version of static response functions. In this way, useful quantities such as self and mutual polarizabilities originally defined through the HMO parameters can be redefined as self and mutual softnesses. The model is illustrated by discussing the classical Hammett free energy relationship describing inductive substituent effects on the reactivity of benzoic acids.

KW - Phenomenological reactivity theory

KW - Self and mutual softnesses

KW - Semi-empirical response functions

UR - http://www.scopus.com/inward/record.url?scp=77951498093&partnerID=8YFLogxK

U2 - 10.1007/s00214-009-0674-1

DO - 10.1007/s00214-009-0674-1

M3 - Article

AN - SCOPUS:77951498093

VL - 126

SP - 45

EP - 54

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

SN - 1432-881X

IS - 1

ER -