Electron Density Analysis of Hyperconjugation.
Hyperconjugation is analyzed through the electron density of orbitals responsible for hyperconjugative interactions, which cannot be detected by means of conventional electron-density-based calculations. This interaction is detected through the π electron density topology, by excluding σ electron density from the total. As the presence of the hyperconjugation phenomenon in carbocation systems is well understood, several carbocations are benchmarked, and the results show that the positive carbon atom establishes a hyperconjugative critical point with the adjacent methyl group(s). Also, π localization and delocalization indices are employed to support the conclusions made by the topological analysis.
Department of Chemistry, College of Sciences, Yasouj University, Yasouj, 75914-353, Iran. azami@yu.ac.ir.
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http://orcid.org/0000-0002-8868-3517
SM
Azami
carbocations; critical point; electron density; hyperconjugation; topological analysis