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σ-Hole bonding: a physical interpretation.

Peter Politzer1, Jane S Murray, Timothy Clark

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This summary is machine-generated.

Covalently bonded atoms create positive "σ-holes" enabling directional interactions. These σ-hole interactions, including halogen and hydrogen bonding, are Coulombic and influenced by potential magnitudes and polarizabilities.

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Area of Science:

  • Chemistry
  • Materials Science
  • Physics

Background:

  • Anisotropic electronic densities in Group IV-VII atoms create positive electrostatic potential regions.
  • These positive regions, termed 'σ-holes,' are located on the extensions of covalent bonds.
  • Such σ-holes facilitate attractive and directional interactions with electron-rich sites.

Purpose of the Study:

  • To elucidate the nature and scope of σ-hole interactions.
  • To establish the relationship between σ-hole interactions, halogen bonding, and hydrogen bonding.
  • To explain the underlying principles governing the strength of these interactions.

Main Methods:

  • Theoretical analysis based on the Hellmann-Feynman theorem.
  • Examination of electrostatic potential distributions in covalently bonded atoms.
  • Consideration of Coulombic forces, including polarization and dispersion effects.

Main Results:

  • σ-holes enable directional interactions with Lewis bases, anions, and π electrons.
  • Halogen bonding is identified as a specific type of σ-hole interaction for Group VII atoms.
  • Hydrogen bonding is presented as a less directional form of σ-hole interaction.
  • Interactions can also occur with positive sites due to coexisting negative potential regions.
  • All interactions are confirmed to be Coulombic in nature.

Conclusions:

  • σ-hole interactions are a fundamental aspect of intermolecular forces in covalently bonded systems.
  • The strength of σ-hole bonding is directly proportional to the potentials of the interacting sites.
  • Polarizability plays a role in modulating the strength of these interactions.