title: σ-Hole bonding: a physical interpretation.
abstract: The anisotropic electronic densities of covalently-bonded Group IV-VII atoms frequently give rise to regions of positive electrostatic potential on the extensions of covalent bonds to these atoms. Through such positive "σ-holes," the atoms can interact attractively and highly directionally with negative sites such as the lone pairs of Lewis bases, anions, π electrons, etc. In the case of Group VII this is called "halogen bonding." Hydrogen bonding can be viewed as a less directional subset of σ-hole interactions. Since positive σ-holes often exist in conjunction with regions of negative potential, the atoms can also interact favorably with positive sites. In accordance with the Hellmann-Feynman theorem, all of these interactions are purely Coulombic in nature (which encompasses polarization and dispersion). The strength of σ-hole bonding increases with the magnitudes of the potentials of the positive σ-hole and the negative site; their polarizabilities must sometimes also be taken explicitly into account.
authors.affiliation: Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA, ppolitze@uno.edu.
authors.forename: Peter
authors.initials: P
authors.lastname: Politzer
authors.forename: Jane S
authors.initials: JS
authors.lastname: Murray
authors.forename: Timothy
authors.initials: T
authors.lastname: Clark