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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
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Intermolecular forces (IMF) are electrostatic attractions arising from charge-charge interactions between molecules. The strength of the intermolecular force is influenced by the distance of separation between molecules. The forces significantly affect the interactions in solids and liquids, where the molecules are close together. In gases, IMFs become important only under high-pressure conditions (due to the proximity of gas molecules). Intermolecular forces dictate the physical properties of...
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Atoms and molecules interact with each other through intermolecular forces. These electrostatic forces arise from attractive or repulsive interactions between particles with permanent, partial, or temporary charges. The intermolecular forces between neutral atoms and molecules are ion–dipole, dipole–dipole, and dispersion forces, collectively known as van der Waals forces.
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The molecular orbital theory describes the distribution of electrons in molecules in a manner similar to the distribution of electrons in atomic orbitals. The region of space in which a valence electron in a molecule is likely to be found is called a molecular orbital. Mathematically, the linear combination of atomic orbitals (LCAO) generates molecular orbitals. Combinations of in-phase atomic orbital wave functions result in regions with a high probability of electron density, while...
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Noncovalent attractions are associations within and between molecules that influence the shape and structural stability of complexes. These interactions differ from covalent bonding in that they do not involve sharing of electrons.
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Intermolecular Covalent Interactions: Nature and Directionality.

Lucas de Azevedo Santos1, Teodorico C Ramalho2,3, Trevor A Hamlin1

  • 1Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS), Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|December 8, 2022
PubMed
Summary

Covalent interactions, not electrostatics, drive the directionality of pnictogen, chalcogen, and halogen bonds. This challenges the traditional σ-hole model, revealing new insights into electron-rich intermolecular forces.

Keywords:
bond theorychalcogen bondsdensity functional calculationshalogen bondspnictogen bonds

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Area of Science:

  • * Computational chemistry and quantum mechanics.
  • * Investigating non-covalent interactions in molecular systems.

Background:

  • * Pnictogen, chalcogen, and halogen bonds are crucial intermolecular forces.
  • * The σ-hole model traditionally explains their directionality via electrostatics.

Purpose of the Study:

  • * To analyze the origin and directionality of pnictogen, chalcogen, and halogen bonds.
  • * To evaluate the validity of the σ-hole model for these interactions.

Main Methods:

  • * Relativistic density functional theory (DFT) calculations.
  • * Kohn-Sham molecular orbital (MO) and energy decomposition analyses (EDA).

Main Results:

  • * Covalence (HOMO-LUMO interactions) significantly contributes to bond energy alongside electrostatics.
  • * Directionality arises from covalence, counteracting electrostatic forces that favor bending.
  • * The σ-hole model fails to explain the observed directionality and electrostatic contributions.

Conclusions:

  • * Intermolecular bond directionality is primarily governed by covalent contributions.
  • * The σ-hole model is insufficient for describing electron-rich interactions.
  • * Findings apply to both anionic and neutral complexes, broadening their scope.