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A Unified View of Halogen Bonding, Hydrogen Bonding and Other σ-Hole Interactions

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Noncovalent Forces

Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 19))

Abstract

The term “σ-hole” refers to a region of diminished electronic density along the extension of a covalent single bond to a hydrogen or an atom of Groups IV—VII. This region often has a positive electrostatic potential through which the atom can interact attractively with a negative site (such as a lone pair of a Lewis base, π electrons or an anion) to form a noncovalent complex. Hydrogen bonding and halogen bonding are the most prominent examples of such σ-hole interactions, although they have long been known experimentally for Groups IV—VI as well (but without the σ-hole label). σ-Holes result from the anisotropic charge distributions of covalently-bonded atoms. It follows from the Hellmann-Feynman theorem that σ-hole interactions can be understood and described as Coulombic, which includes polarization and dispersion. In the context of noncovalent interactions, charge transfer is simply a mathematical formulation of polarization.

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Authors and Affiliations

  1. Department of Chemistry, University of New Orleans, 70148, New Orleans, LA, USA

    Peter Politzer & Jane S. Murray

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  1. Peter Politzer
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  2. Jane S. Murray
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Correspondence to Peter Politzer .

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  1. Department of Chemistry & Biochemistry, Utah State University, Logan, Utah, USA

    Steve Scheiner

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Politzer, P., Murray, J. (2015). A Unified View of Halogen Bonding, Hydrogen Bonding and Other σ-Hole Interactions. In: Scheiner, S. (eds) Noncovalent Forces. Challenges and Advances in Computational Chemistry and Physics, vol 19. Springer, Cham. https://doi.org/10.1007/978-3-319-14163-3_10

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