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Halogen and Chalcogen Bond Energies Evaluated Using Electron Density Properties.

Antonio Bauzá1, Antonio Frontera1

  • 1Department of Chemistry, Universitat de les Illes Balears, Crta. de Valldemossa km 7.7, 07122, Palma de Mallorca (Baleares), Spain.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|December 12, 2019
PubMed
Summary

This study reveals strong linear relationships between halogen/chalcogen bond energies and local energy densities. These findings enable accurate estimation of interaction energies for both intermolecular and intramolecular bonds.

Keywords:
chalcogen bondingenergy predictionhalogen bondingmolecular recognition“atoms-in-molecules”

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Area of Science:

  • Computational chemistry
  • Supramolecular chemistry
  • Chemical bonding theory

Background:

  • Halogen bonds (X-bonds) and chalcogen bonds (Ch-bonds) are crucial non-covalent interactions.
  • Understanding these interactions is key to predicting molecular behavior and designing new materials.
  • Quantifying bond energies often requires computationally intensive methods.

Purpose of the Study:

  • To investigate the relationship between interaction energies and local electronic properties for X-bonds and Ch-bonds.
  • To develop a predictive model for estimating bond energies based on local energy densities.
  • To explore the applicability of this model to both intermolecular and intramolecular interactions.

Main Methods:

  • Calculated interaction energies for 36 complexes involving heavier halogens (Br, I) and chalcogens (Se, Te) using RI-MP2/def2-TZVP.
  • Analyzed local kinetic energy densities (G(r)) and potential energy densities (V(r)) at bond critical points.
  • Investigated linear correlations between interaction energies and energy densities.

Main Results:

  • Identified strong linear relationships between X-bond and Ch-bond energies and V(r) energy density.
  • Demonstrated that interaction energies can be estimated without monomer calculations.
  • Showed the model's utility for intramolecular X/Ch-bonds.
  • Found a unified correlation applicable to both halogen and chalcogen bonding.

Conclusions:

  • Local energy densities, particularly V(r), provide a reliable method for estimating X-bond and Ch-bond strengths.
  • This approach simplifies energy calculations and aids in understanding intramolecular interactions.
  • A single empirical correlation can effectively describe both halogen and chalcogen bonding, unifying their predictive models.