Premium
Electron Density Analysis of Hyperconjugation
Author(s) -
Azami S. M.
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500842
Subject(s) - hyperconjugation , carbocation , chemistry , delocalized electron , electron density , atomic orbital , electron localization function , atom (system on chip) , computational chemistry , density functional theory , electron , chemical physics , physics , photochemistry , molecule , quantum mechanics , organic chemistry , computer science , embedded system
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.