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Van der Waals Interactions01:24

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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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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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The ideal gas law is an approximation that works well at high temperatures and low pressures. The van der Waals equation of state (named after the Dutch physicist Johannes van der Waals, 1837−1923) improves it by considering two factors.
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Many-body van der Waals interactions beyond the dipole approximation.

Dario Massa1, Alberto Ambrosetti1, Pier Luigi Silvestrelli1

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This study introduces a comprehensive many-body approach for van der Waals (vdW) interactions beyond simple dipole approximations. It reveals that combined multipolar and many-body effects are crucial for accurately describing interactions in large molecular and nanoscale systems.

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Area of Science:

  • Computational chemistry
  • Materials science
  • Condensed matter physics

Background:

  • Long-ranged van der Waals (vdW) interactions are fundamental in molecular and nanoscale systems.
  • Current models, like Lennard-Jones, often rely on two-body and dipolar approximations.
  • The combined effects of beyond-dipole interactions and many-body contributions remain poorly understood, particularly for large systems.

Purpose of the Study:

  • To develop and present a full many-body description of van der Waals (vdW) interactions that extends beyond the dipole approximation.
  • To create a method efficiently applicable to large-scale molecular and nanoscale systems.
  • To investigate the interplay between multipolar terms and many-body effects in vdW interactions.

Main Methods:

  • Development of a theoretical framework for many-body van der Waals interactions.
  • Inclusion of beyond-dipole terms, specifically dipole-quadrupole interactions.
  • Application of the method to large-scale molecular and nanoscale systems.
  • Analysis of many-body screening effects on vdW interactions.

Main Results:

  • Dipole-quadrupole interactions are shown to be significant even at nanometer-scale separations.
  • Many-body effects introduce system-dependent screening, substantially reducing vdW interactions.
  • The developed many-body, multipolar approach provides a more accurate description compared to traditional methods.
  • The findings highlight the importance of considering both many-body and multipolar effects concurrently.

Conclusions:

  • A complete many-body description beyond the dipole approximation is essential for accurate vdW interaction calculations.
  • Combined many-body and multipolar terms are critical for understanding vdW forces in complex molecular and nanoscale systems.
  • This work offers a reliable computational tool for investigating vdW interactions in systems previously challenging to model.