Valence Bond Description of Halogen Bonding
Résumé
The chapter describes the Valence Bond view of halogen bonding, outlining the results obtained through BOVB and Spin-Coupled studies. VB theory confirms, on a rigorous ab initio basis, previously proposed models developed on simple and intuitive chemical concepts. BOVB calculations demonstrate quantitatively the importance of charge transfer to the interaction, consistently with the Mulliken model. Analysis of the Spin-Coupled orbitals proves the existence of the σ-hole on the halogen atom, in agreement with the Politzer model, and points to a VB picture of halogen bonding as due to a shift/delocalization of the Lewis base lone pair towards the halogen atom.
Mots clés
σ-hole
BOVB theory
Charge transfer interactions
Electrostatic interactions
Energy decomposition schemes
Halogen bonding
Intermolecular interactions
Mulliken model of halogen bonding
Politzer model of halogen bonding
Spin-Coupled orbitals deformation
Spin-Coupled orbitals overlap
Spin-Coupled theory X-ray restrained
Spin-Coupled (XR-SC) approach