Conrotatory and disrotatory pathways in the electrocyclic isomerization of cyclobutene to cis-butadiene: The spin-coupled viewpoint

J M  Oliva; J  Gerratt; P B  Karadakov; D L  Cooper

Conrotatory and disrotatory pathways in the electrocyclic isomerization of cyclobutene to cis-butadiene: The spin-coupled viewpoint

J M Oliva, J Gerratt, P B Karadakov, D L Cooper

Chemistry

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

Abstract

Spin-coupled theory is used to study the changes which occur in the electronic wave function as a system moves along the intrinsic reaction coordinate (IRC) for the case of conrotatory and disrotatory motion in the ground-state electrocyclic interconversion of cyclobutene to cis-butadiene. It is shown that the reaction is already well under way in the conrotatory case at the transition point (considerable cis-butadiene character), but the system still retains an overwhelming reactant (cyclobutene) character for the disrotatory motion. In both the conrotatory and disrotatory cases, the sharp changes in the weights of the two spin couplings, associated with the onset of bond breaking or bond formation, are shown to occur at points along the IRC well after the transition point. (C) 1997 American Institute of Physics.

Original language	English
Pages (from-to)	8917-8926
Number of pages	10
Journal	Journal of Chemical Physics
Volume	107
Issue number	21
Publication status	Published - 1 Dec 1997

Keywords

VALENCE BOND THEORY
TRANSFORMATION
AROMATICITY

Cite this

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title = "Conrotatory and disrotatory pathways in the electrocyclic isomerization of cyclobutene to cis-butadiene: The spin-coupled viewpoint",

abstract = "Spin-coupled theory is used to study the changes which occur in the electronic wave function as a system moves along the intrinsic reaction coordinate (IRC) for the case of conrotatory and disrotatory motion in the ground-state electrocyclic interconversion of cyclobutene to cis-butadiene. It is shown that the reaction is already well under way in the conrotatory case at the transition point (considerable cis-butadiene character), but the system still retains an overwhelming reactant (cyclobutene) character for the disrotatory motion. In both the conrotatory and disrotatory cases, the sharp changes in the weights of the two spin couplings, associated with the onset of bond breaking or bond formation, are shown to occur at points along the IRC well after the transition point. (C) 1997 American Institute of Physics.",

keywords = "VALENCE BOND THEORY, TRANSFORMATION, AROMATICITY",

author = "Oliva, {J M} and J Gerratt and Karadakov, {P B} and Cooper, {D L}",

year = "1997",

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TY - JOUR

T1 - Conrotatory and disrotatory pathways in the electrocyclic isomerization of cyclobutene to cis-butadiene: The spin-coupled viewpoint

AU - Oliva, J M

AU - Gerratt, J

AU - Karadakov, P B

AU - Cooper, D L

PY - 1997/12/1

Y1 - 1997/12/1

N2 - Spin-coupled theory is used to study the changes which occur in the electronic wave function as a system moves along the intrinsic reaction coordinate (IRC) for the case of conrotatory and disrotatory motion in the ground-state electrocyclic interconversion of cyclobutene to cis-butadiene. It is shown that the reaction is already well under way in the conrotatory case at the transition point (considerable cis-butadiene character), but the system still retains an overwhelming reactant (cyclobutene) character for the disrotatory motion. In both the conrotatory and disrotatory cases, the sharp changes in the weights of the two spin couplings, associated with the onset of bond breaking or bond formation, are shown to occur at points along the IRC well after the transition point. (C) 1997 American Institute of Physics.

AB - Spin-coupled theory is used to study the changes which occur in the electronic wave function as a system moves along the intrinsic reaction coordinate (IRC) for the case of conrotatory and disrotatory motion in the ground-state electrocyclic interconversion of cyclobutene to cis-butadiene. It is shown that the reaction is already well under way in the conrotatory case at the transition point (considerable cis-butadiene character), but the system still retains an overwhelming reactant (cyclobutene) character for the disrotatory motion. In both the conrotatory and disrotatory cases, the sharp changes in the weights of the two spin couplings, associated with the onset of bond breaking or bond formation, are shown to occur at points along the IRC well after the transition point. (C) 1997 American Institute of Physics.

KW - VALENCE BOND THEORY

KW - TRANSFORMATION

KW - AROMATICITY

M3 - Article

SN - 0021-9606

VL - 107

SP - 8917

EP - 8926

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 21

ER -