σ-hole bonding between like atoms; a fallacy of atomic charges

• DOI: 10.1007/s00894-008-0280-5
• Publication Date: 2008-03-03T12:10:41Z
• Authors: Peter Politzer; Jane S. Murray; Monica C. Concha
• Keywords: Atomic charge; Atoms in molecules; Non-covalent interactions; Electrostatics

Covalently bonded atoms, at least in Groups V-VII, may have regions of both positive and negative electrostatic potentials on their surfaces. The positive regions tend to be along the extensions of the bonds to these atoms; the origin of this can be explained in terms of the sigma-hole concept. It is thus possible for such an atom in one molecule to interact electrostatically with its counterpart in a second, identical molecule, forming a highly directional noncovalent bond. Several examples are presented and discussed. Such "like-like" interactions could not be understood in terms of atomic charges assigned by any of the usual procedures, which view a bonded atom as being entirely positive or negative.