Intermolecular force

Intermolecular force is the force that mediates interaction between molecules, including the electromagnetic forces of attraction or repulsion which act between atoms and other types of neighboring particles, e.g. atoms or ions. Intermolecular forces are weak relative to intramolecular forces – the forces which hold a molecule together.

For example, the covalent bond, involving sharing electron pairs between atoms, is much stronger than the forces present between neighboring molecules. Both sets of forces are essential parts of force fields frequently used in molecular mechanics.

The investigation of intermolecular forces starts from macroscopic observations which indicate the existence and action of forces at a molecular level. These observations include non-ideal-gas thermodynamic behavior reflected by virial coefficients, vapor pressure, viscosity, superficial tension, and absorption data.

The first reference to the nature of microscopic forces is found in Alexis Clairaut’s work Théorie de la figure de la Terre, published in Paris in 1743. Other scientists who have contributed to the investigation of microscopic forces include: Laplace, Gauss, Maxwell and Boltzmann.

Attractive intermolecular forces are categorized into the following types:

Hydrogen bonding:

A hydrogen bond is the attraction between the lone pair of an electronegative atom and a hydrogen atom that is bonded to an electronegative atom, usually nitrogen, oxygen, or fluorine. The hydrogen bond is often described as a strong electrostatic dipole–dipole interaction. However, it also has some features of covalent bonding: it is directional, stronger than a van der Waals force interaction, produces interatomic distances shorter than the sum of their van der Waals radii, and usually involves a limited number of interaction partners, which can be interpreted as a kind of valence.

Ion–induced dipole forces:

The attraction between cationic and anionic sites is a noncovalent, or intermolecular interaction which is usually referred to as ion pairing or salt bridge. It is essentially due to electrostatic forces, although in aqueous medium the association is driven by entropy and often even endothermic. Most salts form crystals with characteristic distances between the ions; in contrast to many other noncovalent interactions, salt bridges are not directional and show in the solid state usually contact determined only by the van der Waals radii of the ions.

Ion–dipole forces

Ion–dipole and ion–induced dipole forces are similar to dipole–dipole and dipole–induced dipole interactions but involve ions, instead of only polar and non-polar molecules. Ion–dipole and ion–induced dipole forces are stronger than dipole–dipole interactions because the charge of any ion is much greater than the charge of a dipole moment. Ion–dipole bonding is stronger than hydrogen bonding.

And van der Waals forces – Keesom force, Debye force, and London dispersion force

Intermolecular forces observed between atoms and molecules can be described phenomenologically as occurring between permanent and instantaneous dipoles. Alternatively, one may seek a fundamental, unifying theory that is able to explain the various types of interactions such as hydrogen bonding, van der Waals forces and dipole–dipole interactions.

Typically, this is done by applying the ideas of quantum mechanics to molecules, and Rayleigh–Schrödinger perturbation theory has been especially effective in this regard. When applied to existing quantum chemistry methods, such a quantum mechanical explanation of intermolecular interactions provides an array of approximate methods that can be used to analyze intermolecular interactions.

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