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Orbital topology. I. A basic topological model for chemical systems, an orbital mapping...
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Orbital topology. I. A basic topological model for chemical systems, an orbital mapping technique, and analyses of model, thermal electrocyclic reactions
作者:
Donald R. Kelsey,
期刊:
Journal of Computational Chemistry
(WILEY Available online 1980)
卷期:
Volume 1,
issue 1
页码: 3-20
ISSN:0192-8651
年代: 1980
DOI:10.1002/jcc.540010102
出版商: John Wiley&Sons, Inc.
数据来源: WILEY
摘要:
AbstractA topological model which provides a unifying framework for chemical reactions and molecular structure is proposed. Such basic concepts as overlap, orthogonality, reaction continuity, reaction reversibility, and orbital correspondence are incorporated into the model in a logical fashion. A chemical reaction pathway is regarded as a function that transforms a reactant topological space into its equivalent product space. The unique character usually ascribed to reactants, products, and their wavefunctions is superfluous. The model also allows considerable approximation of the wavefunctions and the reaction pathway without affecting the overall result. A simple orbital mapping technique consistent with the model which traces the transformation of orbitals usingintermolecular overlaps of the orbitals is also proposed. The suitability of a given pathway (“allowed” or “forbidden”) can be deduced explicitly without invoking symmetry (or other) rules and without resorting to detailed calculation of reaction energy surfaces. The validity of the mapping procedure has been confirmed by several thermal electrocyclic reactions: the ring‐opening isomerizations of substituted cyclopropyl cations, cyclopropyl anion, cyclopropanone, cyclobutene, benzocyclobutene, Dewar benzenes, and 1,3‐cyclohexadiene. Orbital mapping with EHT and CNDO/2 MOs correctly predicts the reaction stereochemistry (conrotatory or disrotatory) in
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