AROMATIC ELECTROPHILIC SUBSTITUTION - A MODERN VALENCE-BOND STUDY

G  RAOS; J  GERRATT; P B  KARADAKOV; D L  COOPER; M  RAIMONDI

AROMATIC ELECTROPHILIC SUBSTITUTION - A MODERN VALENCE-BOND STUDY

G RAOS, J GERRATT, P B KARADAKOV, D L COOPER, M RAIMONDI

Chemistry

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

Abstract

The Hartree-Fock, spin-coupled valence bond and complete active space self-consistent field methods are used to study the electronic structure of benzene, phenol, benzonitrile and their protonated arenium intermediates. The spin-coupled wavefunctions for these systems can be readily interpreted in terms of the well known classical valence bond resonance structures. However, the charge delocalization in the arenium ions is not achieved through a resonance mechanism which must be invoked if a localized orbital description is adopted, but through a single spatial configuration of semi-delocalized orbitals. The effect of the substituents on the energy and the electron distribution of the arenium intermediates is borne out in a clear and visual way by the form of a spin-coupled wavefunction for these systems.

Original language	English
Pages (from-to)	4011-4030
Number of pages	20
Journal	JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS
Volume	91
Issue number	22
Publication status	Published - 21 Nov 1995

Keywords

MOLECULAR-ORBITAL THEORY
SPIN-COUPLED DESCRIPTION
ELECTRONIC-STRUCTURE
ORGANIC COMPOUNDS
BENZENE
METHANE
ETHENE
ATOMS
CH2

Cite this

@article{0e1453310a174aafa8fbd56f81d452a1,

title = "AROMATIC ELECTROPHILIC SUBSTITUTION - A MODERN VALENCE-BOND STUDY",

abstract = "The Hartree-Fock, spin-coupled valence bond and complete active space self-consistent field methods are used to study the electronic structure of benzene, phenol, benzonitrile and their protonated arenium intermediates. The spin-coupled wavefunctions for these systems can be readily interpreted in terms of the well known classical valence bond resonance structures. However, the charge delocalization in the arenium ions is not achieved through a resonance mechanism which must be invoked if a localized orbital description is adopted, but through a single spatial configuration of semi-delocalized orbitals. The effect of the substituents on the energy and the electron distribution of the arenium intermediates is borne out in a clear and visual way by the form of a spin-coupled wavefunction for these systems.",

keywords = "MOLECULAR-ORBITAL THEORY, SPIN-COUPLED DESCRIPTION, ELECTRONIC-STRUCTURE, ORGANIC COMPOUNDS, BENZENE, METHANE, ETHENE, ATOMS, CH2",

author = "G RAOS and J GERRATT and KARADAKOV, {P B} and COOPER, {D L} and M RAIMONDI",

year = "1995",

month = nov,

day = "21",

language = "English",

volume = "91",

pages = "4011--4030",

journal = "JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS",

issn = "0956-5000",

publisher = "The Royal Society of Chemistry",

number = "22",

}

TY - JOUR

T1 - AROMATIC ELECTROPHILIC SUBSTITUTION - A MODERN VALENCE-BOND STUDY

AU - RAOS, G

AU - GERRATT, J

AU - KARADAKOV, P B

AU - COOPER, D L

AU - RAIMONDI, M

PY - 1995/11/21

Y1 - 1995/11/21

N2 - The Hartree-Fock, spin-coupled valence bond and complete active space self-consistent field methods are used to study the electronic structure of benzene, phenol, benzonitrile and their protonated arenium intermediates. The spin-coupled wavefunctions for these systems can be readily interpreted in terms of the well known classical valence bond resonance structures. However, the charge delocalization in the arenium ions is not achieved through a resonance mechanism which must be invoked if a localized orbital description is adopted, but through a single spatial configuration of semi-delocalized orbitals. The effect of the substituents on the energy and the electron distribution of the arenium intermediates is borne out in a clear and visual way by the form of a spin-coupled wavefunction for these systems.

AB - The Hartree-Fock, spin-coupled valence bond and complete active space self-consistent field methods are used to study the electronic structure of benzene, phenol, benzonitrile and their protonated arenium intermediates. The spin-coupled wavefunctions for these systems can be readily interpreted in terms of the well known classical valence bond resonance structures. However, the charge delocalization in the arenium ions is not achieved through a resonance mechanism which must be invoked if a localized orbital description is adopted, but through a single spatial configuration of semi-delocalized orbitals. The effect of the substituents on the energy and the electron distribution of the arenium intermediates is borne out in a clear and visual way by the form of a spin-coupled wavefunction for these systems.

KW - MOLECULAR-ORBITAL THEORY

KW - SPIN-COUPLED DESCRIPTION

KW - ELECTRONIC-STRUCTURE

KW - ORGANIC COMPOUNDS

KW - BENZENE

KW - METHANE

KW - ETHENE

KW - ATOMS

KW - CH2

M3 - Article

SN - 0956-5000

VL - 91

SP - 4011

EP - 4030

JO - JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS

JF - JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS

IS - 22

ER -