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The Nature of Resonance in Allyl Ions and Radical
Linköping University, The Institute of Technology. Linköping University, Department of Physics, Chemistry and Biology, Computational Physics .
Aix Marseille University.
University of Paris.
2008 (English)In: JOURNAL OF PHYSICAL CHEMISTRY A, ISSN 1089-5639 , Vol. 112, no 50, 13249-13255 p.Article in journal (Refereed) Published
Abstract [en]

A recent valence bond scheme based on Lewis structures, the valence bond BOND (VBB) method (BOND: Breathing Orbitals Naturally Delocalized) method (Linares, M.; Braida, B.; Humbel, S. J. Phys. Chem. A 2006, 110, 2505-2509), is applied to explore the nature of resonance in allyl systems. Whereas allyl radical is correctly described by the resonance between the two traditional Lewis structures, a third "long-bonded" structure, which apparently creates a pi bond between the two distant carbon atoms, appears to plays an important role in allyl ions description. The similar vertical resonance energy (VRE) for both allyl ions is rather moderate (similar to 37 kcal/mol) in the two-structure description but is significantly enhanced when the long-bonded structure is included into the VBB wave function (by up to 20 kcal/mol). The allyl radical is much less resonant and is correctly described by the traditional two-structure picture. The development of VBB Lewis structures into "pure" valence bond determinants enlightens the role of the third structure in the description of allyl ions. The existence of a long bond between the two distant carbon atoms is clearly ruled out. Charge equilibration effect is shown to be a minor factor. The third structure is finally attributed to one- and three-electron bonding character revealed in the g systems of the cation and anion, respectively. This makes these systems two surprising examples of odd electron bonding within a singlet state. Last, the two-structure description of allyl radical is improved by addition of missing ionic structures.

Place, publisher, year, edition, pages
2008. Vol. 112, no 50, 13249-13255 p.
National Category
Natural Sciences
URN: urn:nbn:se:liu:diva-16249DOI: 10.1021/jp8038169OAI: diva2:133518
Available from: 2009-01-12 Created: 2009-01-09 Last updated: 2009-02-16

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Linares, Mathieu
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The Institute of TechnologyComputational Physics
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