intermolecular forces, forces that are exerted by molecules on each other and that, in general, affect the macroscopic properties of the material of which the molecules are a part. Such forces may be either attractive or repulsive in nature. They are conveniently divided into two classes: short-range forces, which operate when the centers of the molecules are separated by 3 angstroms or less, and long-range forces, which operate at greater distances. Generally, if molecules do not tend to interact chemically, the short-range forces between them are repulsive. These forces arise from interactions of the electrons associated with the molecules and are also known as exchange forces. Molecules that interact chemically have attractive exchange forces; these are also known as valence forces. Mechanical rigidity of molecules and effects such as limited compressibility of matter arise from repulsive exchange forces. Long-range forces, or van der Waals forces as they are also called, are attractive and account for a wide range of physical phenomena, such as friction, surface tension, adhesion and cohesion of liquids and solids, viscosity, and the discrepancies between the actual behavior of gases and that predicted by the ideal gas law. Van der Waals forces arise in a number of ways, one being the tendency of electrically polarized molecules to become aligned. Quantum theory indicates also that in some cases the electrostatic fields associated with electrons in neighboring molecules constrain the electrons to move more or less in phase.
The Columbia Electronic Encyclopedia, 6th ed. Copyright © 2012, Columbia University Press. All rights reserved.