intermolecular forces


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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 angstromsangstrom
, abbr. Å, unit of length equal to 10−10 meter (0.0000000001 meter); it is used to measure the wavelengths of visible light and of other forms of electromagnetic radiation, such as ultraviolet radiation and X rays.
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 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 frictionfriction,
resistance offered to the movement of one body past another body with which it is in contact. In certain situations friction is desired. Without friction the wheels of a locomotive could not "grip" the rails nor could power be transmitted by belts.
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, surface tensionsurface tension,
tendency of liquids to reduce their exposed surface to the smallest possible area. A drop of water, for example, tends to assume the shape of a sphere. The phenomenon is attributed to cohesion, the attractive forces acting between the molecules of the liquid
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, adhesion and cohesionadhesion and cohesion,
attractive forces between material bodies. A distinction is usually made between an adhesive force, which acts to hold two separate bodies together (or to stick one body to another) and a cohesive force, which acts to hold together the like or unlike
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 of liquids and solids, viscosityviscosity,
resistance of a fluid to flow. This resistance acts against the motion of any solid object through the fluid and also against motion of the fluid itself past stationary obstacles.
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, and the discrepancies between the actual behavior of gases and that predicted by the ideal gas lawgas laws,
physical laws describing the behavior of a gas under various conditions of pressure, volume, and temperature. Experimental results indicate that all real gases behave in approximately the same manner, having their volume reduced by about the same proportion of the
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. 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.

Intermolecular forces

Attractive or repulsive interactions that occur between all atoms and molecules. Intermolecular forces become significant at molecular separations of about 1 nanometer or less, but are much weaker than the forces associated with chemical bonding. They are important, however, because they are responsible for many of the physical properties of solids, liquids, and gases. These forces are also largely responsible for the three-dimensional arrangements of biological molecules and polymers.

Intermolecular forces can be classified into several types, of which two are universal. The attractive force known as dispersion arises from the quantum-mechanical fluctuation of the electron density around the nucleus of each atom. At distances greater than 1 nm or so, the electrons of each atom move independently of the other, and the charge distribution is spherically symmetric. At shorter distances, an instantaneous fluctuation of the charge density in one atom can affect the other. If the electrons of one atom move briefly to the side nearer the other, the electrons of the other atom are repelled to the far side. In this configuration, both atoms have a small dipole moment, and they attract each other electrostatically. At another moment, the electrons may move the other way, but their motions are correlated so that an attractive force is maintained on average. Molecular orbital theory shows that the electrons of each atom are slightly more likely to be on the side nearer to the other atom, so that each atomic nucleus is attracted by its own electrons in the direction of the other atom.

At small separations the electron clouds can overlap, and repulsive forces arise. These forces are described as exchange-repulsion, and are a consequence of the Pauli exclusion principle, a quantum-mechanical effect which prevents electrons from occupying the same region of space simultaneously. To accommodate it, electrons are squeezed out from the region between the nuclei, which repel each other as a result. Each element can be assigned, approximately, a characteristic van der Waals radius; that is, when atoms in different molecules approach more closely than the sum of their radii, the repulsion ennergy increases sharply. It is this effect that gives molecules their characteristic shape, leading to steric effects in chemical reactions. See Exclusion principle

The other important source of intermolecular forces is the electrostatic interaction. When molecules are formed from atoms, electrons flow from electropositive atoms to electronegative ones, so that the atoms become somewhat positively or negatively charged. In addition, the charge distribution of each atom may be distorted by the process of bond formation, leading to atomic dipole and quadrupole moments. The electrostatic interaction between these is an important source of intermolecular forces, especially in polar molecules, but also in molecules that are not normally thought of as highly polar. The electrostatic field of a molecule may cause polarization of its neighbors, and this leads to a further induction contribution to the intermolecular interaction. An induction interaction can often polarize both molecules in such a way as to favor interactions with further molecules, leading to a cooperative network of intermolecular attractions. This effect is important in the network structure of water and ice.

Intermolecular forces are responsible for many of the bulk properties of matter in all its phases. A realistic description of the relationship between pressure, volume, and temperature of a gas must include the effects of attractive and repulsive forces between molecules. The viscosity, diffusion, and surface tension of liquids are examples of physical properties which depend strongly on intermolecular forces. Intermolecular forces are also responsible for the ordered arrangement of molecules in solids, and account for their elasticity and properties (such as the velocity of sound in materials).

References in periodicals archive ?
Figure 3 shows, in long wave approximation, the soft branches of the dispersion relation for [[GAMMA] = 1 in the absence of intermolecular forces ([PHI] = 0) and for [PHI] = 0.
Notice that what is really changing here is not the nature of the statistic to be considered, but the experimental measure of the stage of deformation characterizing the ensembles of equilibrium intermolecular forces inside rubber.
The ability to determine the crystal structures of small organic materials that suffer from poor crystal growth is essential if reliable conclusions are to be drawn from systematic structural studies of intermolecular forces.
1954) when molecules collide with each other in the presence of the Lennard-Jones intermolecular force field.
The nucleation effect may be attributed to hydrogen bonding and other strong intermolecular forces acting between PHB and the HBP due to the high concentration of hydroxyl groups in the outer shell of the HBP.
2]band and C-O strain are sensitive for changes in crystalline nature of cellulose, which originates from intermolecular forces between neighboring chains , as already explained earlier.
When a gecko gloms a foot onto a surface, the billion-or-so spatulae that carpet its sole snuggle so close to the surface that intermolecular forces such as van der Waals bonds may come into play, the researchers say.
The next topic is bonding and intermolecular forces.
These motions are caused by the intermolecular forces exerted by neighboring molecules and resemble the thermal motions of molecules in a liquid.
In addition, measured experimental basicities and affinities are essential to computational chemists for the validation, calibration and establishment of reliable computational methods for quantifying and explaining intermolecular forces and the chemical bond.
The surface tension (surface Gibbs free energy per area) is a direct manifestation of the intermolecular forces.
Liquid films become prone to spinodal dewetting, physicists say, when intermolecular forces add up to a net attraction that tugs the top of the film toward the underlying surface.

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