Abstract
A molecular orbital (MO) interpretation of a chemical reaction, A + B →AB, results from the study of the relationship between the MO’s of AB and those of A and B. In perturbational molecular orbital (PMO) analysis this relationship is examined from the viewpoint of perturbation theory, 1-4 which leads to the concept of orbital interaction that has provided substantial insight into the specificity of chemical reaction. In describing the electronic structure of a single molecule this orbital interaction analysis has been of great utility as well. That is, when a molecule is regarded as an assembly of molecular fragments, it becomes possible to describe the molecular electronic structure as a result of orbital interactions among the molecular fragments. The perturbation behind those interactions is that separate molecules or molecular fragments were brought together in close proximity, and hence may be termed an inter-system perturbation.
Theoretical and conceptual aspects of PMO analysis appropriate for inter- and intra-system perturbations were discussed within the framework of SCF MO theory.
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© 1981 D. Reidel Publishing Company, Dordrecht, Holland
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Whangbo, MH. (1981). Perturbational Molecular Orbital Analysis. In: Csizmadia, I.G., Daudel, R. (eds) Computational Theoretical Organic Chemistry. NATO Advanced Study Institutes Series, vol 67. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-8472-1_12
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DOI: https://doi.org/10.1007/978-94-009-8472-1_12
Publisher Name: Springer, Dordrecht
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