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WIREs Comput Mol Sci
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The many faces of halogen bonding: a review of theoretical models and methods

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Halogen bonds, the formally noncovalent interactions where the halogen acts as a Lewis acid, have brought several controversies to the theoretical world regarding its nature and components, e.g., charge transfer (CT), electrostatics, dispersion, and polarization. The debate on whether all characteristics are accounted for by electrostatics is examined, highlighting the importance of the CT and repulsive interactions. A number of strongly halogen‐bonded complexes are as covalent as metal–ligand coordination bonds. Different levels of computational methods are reviewed with the objective of finding the best accuracy/cost ratios. The unusual electronic anisotropy of the halogen donor and its interaction with a Lewis base demand specific calculation schemes. From the wave‐function theory methods, only the ones with empirical corrections (spin‐component‐scaled MP2 or CCSD, and MP2.5) are suitable when CCSD(T) is unattainable. Density functional theory functionals with a high amount of exact exchange are fast and reliable methods for halogen bonds, but double hybrids are more robust if other types of interactions are involved. Molecular mechanics methods can be useful, but only when specific corrections are added to compensate for the inability of such methods to describe CT. The most common method introduces a virtual site with a partial positive charge to account for the quantum chemical effect of the halogen bond. This methodology has been successfully applied to study protein–ligand interactions for drug design. WIREs Comput Mol Sci 2014, 4:523–540. doi: 10.1002/wcms.1189 This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Computational Biochemistry and Biophysics Theoretical and Physical Chemistry > Thermochemistry
Orbital interaction diagrams for (a) halogen bonds and (b) hydrogen bonds arising in DX···A and DH···A. Only the σ‐interactions are shown.
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Figure showing two rings connected via Br···N halogen bonding.
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Computed protein–ligand structure for the wild‐type HIV‐1 reverse transcriptase. The possible halogen‐bonding interaction with Pro95 is highlighted with the dashed arrow. (Reprinted with permission from Ref , Copyright 2012, American Chemical Society)
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(Top) Schematic figure of a halogen bond where the gray shaded area represents the σ‐hole. (Bottom) Virtual‐site model representing the σ‐hole and the green area shows the Lennard–Jones sphere.
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Dissociation curves for XB parametrized interactions at the MP2 (dotted black line), PM6‐D2 (red), and the PM6‐D2X (blue) levels. (Reprinted with permission from Ref , Copyright 2011, Elsevier)
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RMSD (root mean square deviation) and MSE (mean signed error) in kcal/mol for the (a) VnZ basis sets (n = 2, 3, 4), with or without counterpoise (CP) correction, for the ωB97X and B3LYP functionals. The reference (an almost ‘complete basis set’) was aVQZ+CP. (Reprinted with permission from Ref , Copyright 2013, American Chemical Society)
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Root mean square deviation (RMSD) and mean signed error (MSE) for selected density functional theory (DFT) methods in kcal/mol, for the dissociation energy of the XB51 set, with aVTZ+CP basis set. (Reprinted with permission from Ref , Copyright 2013, American Chemical Society)
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Schematic graph depicting the ‘Pauling point’ of accuracy, first showed by Löwdin in 1985. Note the multiple maxima that can be found in the process of refining the theory. (Reprinted with permission from Ref , Copyright 1985, Wiley)
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Structure and Mechanism > Computational Biochemistry and Biophysics
Structure and Mechanism > Molecular Structures
Theoretical and Physical Chemistry > Thermochemistry

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