A simple model for halogen bonds

2018 ◽  
Author(s):  
Robert A. Shaw ◽  
Grant Hill
Keyword(s):  
Simple Model ◽  
Statistical Model ◽  
Halogen Bond ◽  
Coupled Cluster ◽  
Interaction Energies ◽  
Halogen Bonds ◽  
Bond Interaction ◽  
Explicitly Correlated ◽  
Equilibrium Geometries

In this article we develop a simple statistical model for the prediction of halogen bond interaction energies at equilibrium geometries. The model is based on explicitly correlated coupled cluster results and produces root-mean-squared deviations of 0.14 and 0.28 kcal mol<sup>–1</sup> over separate fitting and validation sets, respectively. We also show how the model can be used to highlight cases where induction or dispersion significantly affect the underlying nature of the interaction.<br>

A simple model for halogen bonds

2018 ◽  
Author(s):  
Robert A. Shaw ◽  
Grant Hill
Keyword(s):  
Simple Model ◽  
Statistical Model ◽  
Halogen Bond ◽  
Coupled Cluster ◽  
Interaction Energies ◽  
Halogen Bonds ◽  
Bond Interaction ◽  
Explicitly Correlated ◽  
Equilibrium Geometries

In this article we develop a simple statistical model for the prediction of halogen bond interaction energies at equilibrium geometries. The model is based on explicitly correlated coupled cluster results and produces root-mean-squared deviations of 0.14 and 0.28 kcal mol<sup>–1</sup> over separate fitting and validation sets, respectively. We also show how the model can be used to highlight cases where induction or dispersion significantly affect the underlying nature of the interaction.<br>

THE COOPERATIVITY BETWEEN HYDROGEN AND HALOGEN BONDS

2008 ◽  
Vol 07 (01) ◽  
pp. 13-35 ◽  
Author(s):  
TIMM LANKAU ◽  
YU-CHUNG WU ◽  
JIAN-WEI ZOU ◽  
CHIN-HUI YU
Keyword(s):  
Simple Model ◽  
Hydrogen Bonds ◽  
Quantum Chemical ◽  
Halogen Bond ◽  
Computational Method ◽  
Halogen Bonds ◽  
Reasonable Accuracy ◽  
Reference Cluster ◽  
Hybrid Functionals ◽  
Two Parameter

The cooperativity between hydrogen bonds and halogen bonds in X–HCN–Y ( X: C2H2, H2O, NH3, HCI, HCN, HF; Y: HF, BrF, Br2 is analyzed with MP2/6-311++G(d, p) and DFT/6-311++G(d, p) calculations using the B3LYP and mPW1PW91 hybrid functionals. The results from the quantum chemical calculations are typically clustered in groups according to the Y-ligand. By choosing the X–HCN–HF group as reference it is possible to describe the interaction between the hydrogen and the halogen bond with a two-parameter model. The value of the first parameter of the model describes the contribution of the X -ligand to the interbond cooperativity in the reference cluster. The second parameter of our model quantifies the changes in interbond cooperativity upon varying the Y -ligand. This simple model can be used to predict the cooperativity in X–HCN–Y trimers with reasonable accuracy and thereby to organize the results systematically. It is further shown that the conclusions drawn from this ordering scheme are independent from the computational method and thereby generally applicable.

scholarly journals Halogen…π Interactions in the Complexes of Fluorenonophane With Haloforms

2021 ◽  
Author(s):  
Svitlana V. Shishkina ◽  
Viktoriya V. Dyakonenko ◽  
Oleg V. Shishkin ◽  
Volodimir P. Semynozhenko ◽  
Tatiana Yu. Bogashchenko ◽  
...  
Keyword(s):  
Halogen Atom ◽  
Halogen Bond ◽  
Bromine Atom ◽  
Quantum Chemical Study ◽  
Halogen Bonding ◽  
Chemical Study ◽  
Interaction Energies ◽  
Halogen Bonds ◽  
Guest Molecules ◽  
True Energy

Abstract The study of two complexes of fluorenonophane with CHCl3 and CHBr3 molecules has revealed that they differ mainly by the halogen bonds between host and guest molecules. The experimental and theoretical quantum chemical study has shown that the strength of a halogen bond depends on the nature of a halogen atom as well as its orientation to the π-system. The more positive electrostatic potential was revealed at the bromine atom indicating the stronger halogen bond with its participation that was confirmed by the interaction energies calculated for corresponding dimers and the evaluation of the true energy of a halogen bond. The orientation of the chlorine atom at the carbon aromatic atom instead of the center of the benzene ring leads to the shortest Hal…C distance that points out the stronger interaction according to the geometrical characteristics. The EDA analysis of the fluorenonophane complexes with CHCl3 and CHBr3 and their analogs with one halogen atom replaced by the hydrogen atom allows us to presume that the nature of halogen bonding is rather dispersive than electrostatic.

scholarly journals A Simple Model for Halogen Bond Interaction Energies

Inorganics ◽  
2019 ◽  
Vol 7 (2) ◽  
pp. 19 ◽  
Author(s):  
Robert Shaw ◽  
J. Hill
Keyword(s):  
Simple Model ◽  
Halogen Bond ◽  
Computational Cost ◽  
Principal Component ◽  
Physical Nature ◽  
Data Sets ◽  
Interaction Energies ◽  
Validation Data ◽  
Equilibrium Separation ◽  
Non Covalent Interactions

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.

scholarly journals Reliable Comparison of Pnicogen, Chalcogen, and Halogen Bonds in Complexes of 6-OXF2-Fulvene (X = As, Sb, Se, Te, Be, I) With Three Electron Donors

2020 ◽  
Vol 8 ◽  
Author(s):  
Na Liu ◽  
Qingzhong Li ◽  
Sean A. C. McDowell
Keyword(s):  
Interaction Energy ◽  
Electrostatic Interaction ◽  
Halogen Bond ◽  
Electron Donors ◽  
Stable Complex ◽  
Interaction Energies ◽  
Halogen Bonds ◽  
Nitrogen Base ◽  
Pnicogen Bond ◽  
Polarization Contribution

The pnicogen, chalcogen, and halogen bonds between 6-OXF2-fulvene (X = As, Sb, Se, Te, Br, and I) and three nitrogen-containing bases (FCN, HCN, and NH3) are compared. For each nitrogen base, the halogen bond is strongest, followed by the pnicogen bond, and the chalcogen bond is weakest. For each type of bond, the binding increases in the FCN &lt; HCN &lt; NH3 pattern. Both FCN and HCN engage in a bond with comparable strengths and the interaction energies of most bonds are &lt; −6 kcal/mol. However, the strongest base NH3 forms a much more stable complex, particularly for the halogen bond with the interaction energy going up to −18 kcal/mol. For the same type of interaction, its strength increases as the mass of the central X atom increases. These bonds are different in strength, but all of them are dominated by the electrostatic interaction, with the polarization contribution important for the stronger interaction. The presence of these bonds changes the geometries of 6-OXF2-fulvene, particularly for the halogen bond formed by NH3, where the F-X-F arrangement is almost vertical to the fulvene ring.

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