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Issue 48, 2017
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The σ-hole revisited

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Abstract

A covalently-bonded atom typically has a region of lower electronic density, a “σ-hole,” on the side of the atom opposite to the bond, along its extension. There is frequently a positive electrostatic potential associated with this region, through which the atom can interact attractively but noncovalently with negative sites. This positive potential reflects not only the lower electronic density of the σ-hole but also contributions from other portions of the molecule. These can significantly influence both the value and also the angular position of the positive potential, causing it to deviate from the extension of the covalent bond. We have surveyed these effects, and their consequences for the directionalities of subsequent noncovalent intermolecular interactions, for atoms of Groups IV–VII. The overall trends are that larger deviations of the positive potential result in less linear intermolecular interactions, while smaller deviations lead to more linear interactions. We find that the deviations of the positive potentials and the nonlinearities of the noncovalent interactions tend to be greatest for atoms of Groups V and VI. We also present arguments supporting the use of the 0.001 a.u. contour of the electronic density as the molecular surface on which to compute the electrostatic potential.

Graphical abstract: The σ-hole revisited

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Publication details

The article was received on 04 Oct 2017, accepted on 21 Nov 2017 and first published on 21 Nov 2017


Article type: Perspective
DOI: 10.1039/C7CP06793C
Citation: Phys. Chem. Chem. Phys., 2017,19, 32166-32178
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    The σ-hole revisited

    P. Politzer, J. S. Murray, T. Clark and G. Resnati, Phys. Chem. Chem. Phys., 2017, 19, 32166
    DOI: 10.1039/C7CP06793C

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