DOI: 10.1002/wcms.1113. σ‐Holes

σ‐Holes

10.1002/wcms.1113

Crossref journal-article

Wiley

WIREs Computational Molecular Science (311)

Abstract

Abstractσ‐Holes are regions of positive molecular electrostatic potential collinear with and opposite to covalent bonds to atoms of Groups IV–VII. They are responsible for many noncovalent bonding interactions, such as halogen bonding. σ‐Holes make ‘negatively charged’ atoms act as if they were ‘positively charged’. The existence of σ‐hole bonding emphasizes what has been called ‘the fallacy of net atomic charges’, which means that many covalently bonded atoms cannot be represented adequately by a single charge because they look negative from some directions and positive from others. Hydrogen bonding can also be regarded as a special case of σ‐hole bonding, although in this case the origin of the σ‐hole is rationalized differently than in the heavier elements. Phenomena such as the directionality of hydrogen bonds and ‘blue‐shifted’ hydrogen bonds can be explained very simply using the σ‐hole concept.This article is categorized under: Structure and Mechanism > Molecular Structures

Bibliography

Clark, T. (2012). ÏâHoles. WIREs Computational Molecular Science, 3(1), 13â20. Portico.

Authors 1

Timothy Clark (first)

References 53 Referenced 222

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{'key': 'e_1_2_8_1_6_1', 'volume-title': 'Halogen Bonding: Fundamentals and Applications, (Structure and Bonding)', 'author': 'Metrangolo P', 'year': '2010'} / Halogen Bonding: Fundamentals and Applications, (Structure and Bonding) by Metrangolo P (2010)
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10.1007/s00894-011-1015-6 / J Mol Model / Halogen bond tunability I: the effects of aromatic fluorine substitution on the strengths of halogen‐bonding interactions involving chlorine, bromine and iodine by Riley KE
10.1021/ja00794a003
{'key': 'e_1_2_8_3_26_2', 'volume-title': 'Molecular Mechanics—ACS Monograph 177', 'author': 'Burkert U', 'year': '1972'} / Molecular Mechanics—ACS Monograph 177 by Burkert U (1972)
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{'key': 'e_1_2_8_3_39_2', 'article-title': 'Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions at attraction in halogen bonds', 'author': 'Riley KE', 'journal-title': 'J Mol Model'} / J Mol Model / Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions at attraction in halogen bonds by Riley KE
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10.1002/anie.201006781
10.1002/jcc.21836
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10.1021/ct300180w / J Chem Theor Comput / Treatment of halogen bonding in the OPLS‐AA force field: application to potent anti‐HIV agents by Jorgensen WL (2012)
10.1021/ci300095x
10.1071/CH10259

Dates

Type	When
Created	13 years ago (Aug. 8, 2012, 12:28 p.m.)
Deposited	1 year, 11 months ago (Sept. 25, 2023, 3:23 a.m.)
Indexed	1 week ago (Aug. 29, 2025, 6:33 a.m.)
Issued	13 years ago (Aug. 8, 2012)
Published	13 years ago (Aug. 8, 2012)
Published Online	13 years ago (Aug. 8, 2012)
Published Print	12 years, 8 months ago (Jan. 1, 2013)

Funders 0

None

BibTeX

@article{Clark_2012, title={σ‐Holes}, volume={3}, ISSN={1759-0884}, url={http://dx.doi.org/10.1002/wcms.1113}, DOI={10.1002/wcms.1113}, number={1}, journal={WIREs Computational Molecular Science}, publisher={Wiley}, author={Clark, Timothy}, year={2012}, month=aug, pages={13–20} }

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