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A Simple Model for Halogen Bond Interaction Energies

Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK
Author to whom correspondence should be addressed.
Inorganics 2019, 7(2), 19;
Received: 18 January 2019 / Revised: 1 February 2019 / Accepted: 6 February 2019 / Published: 10 February 2019
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
Halogen bonds are prevalent in many areas of chemistry, physics, and biology. We present a statistical model for the interaction energies of halogen-bonded systems at equilibrium based on high-accuracy ab initio benchmark calculations for a range of complexes. Remarkably, the resulting model requires only two fitted parameters, X and B—one for each molecule—and optionally the equilibrium separation, R e , between them, taking the simple form E = X B / R e n . For n = 4 , it gives negligible root-mean-squared deviations of 0.14 and 0.28 kcal mol 1 over separate fitting and validation data sets of 60 and 74 systems, respectively. The simple model is shown to outperform some of the best density functionals for non-covalent interactions, once parameters are available, at essentially zero computational cost. Additionally, we demonstrate how it can be transferred to completely new, much larger complexes and still achieve accuracy within 0.5 kcal mol 1 . Using a principal component analysis and symmetry-adapted perturbation theory, we further show how the model can be used to predict the physical nature of a halogen bond, providing an efficient way to gain insight into the behavior of halogen-bonded systems. This means that the model can be used to highlight cases where induction or dispersion significantly affect the underlying nature of the interaction. View Full-Text
Keywords: halogen bond; theoretical chemistry; intermolecular interactions halogen bond; theoretical chemistry; intermolecular interactions
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MDPI and ACS Style

Shaw, R.A.; Hill, J.G. A Simple Model for Halogen Bond Interaction Energies. Inorganics 2019, 7, 19.

AMA Style

Shaw RA, Hill JG. A Simple Model for Halogen Bond Interaction Energies. Inorganics. 2019; 7(2):19.

Chicago/Turabian Style

Shaw, Robert A., and J. Grant Hill. 2019. "A Simple Model for Halogen Bond Interaction Energies" Inorganics 7, no. 2: 19.

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