Theoretical analysis of pi-type hyperconjugative interaction

The critical point (CP) responsible for hyperconjugative interaction is identified, which cannot be detectedby means of conventional electron density based calculations. This CP is detected via π electron density topology, byexcluding σ electron density from the total one. To achieve this, the density matrix is projected onto perpendicular porbitals of the molecular plane. Since the presence of hyperconjugation phenomenon in carbocation systems is wellunderstood, several carbocations are benchmarked and the results show the positive carbon atom establisheshyperconjugative CP with the adjacent methyl group(s). Also, π localization and delocalization indices are employed tosupport the conclusions made by the CP properties.

کلیدواژه ها:

QTAIM ، Hyperconjuagtion ، Critical Point