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Intermolecular forces are forces of attraction or repulsion which act between neighboring particles (atoms,
molecules or ions). They are weak compared to the intramolecular forces, the forces which keep a molecule
together. For example, the covalent bond present within HCl molecules is much stronger than the forces present
between the neighboring molecules, which exist when the molecules are sufficiently close to each other.
If a bond has a H atom directly bonded to either O, N, or F- then it is an H-Bond. If it is polar, then it is a
dipole; if it is nonpolar, then it is a dispersion force (London).
The investigation of intermolecular forces starts from macroscopic observations which point out the existence
and action of forces at molecular level. These observations include non-ideal gas thermodynamic behavior
reflected by virial coefficients, vapor pressure, viscosity, superficial tension and adsorption data.
The first reference to the nature of microscopic forces is found in Alexis Clairaut's work Theorie de la Figure de
la Terre.
[1]
Other scientists who have contributed to the investigation of microscopic forces include: Laplace,
Gauss, Maxwell and Boltzmann.
Attractive intermolecular forces are considered by the following types:
Dipole-dipole forces
Ion-dipole forces
Van der Waals forces (Keesom force, Debye force, and London dispersion force)
Information on intermolecular force is obtained by macroscopic measurements of properties like viscosity, PVT
data. The link to microscopic aspects is given by virial coefficients and Lennard-J ones potentials.
1 Dipole-dipole interactions
1.1 Ion-dipole and ion-induced dipole forces
1.2 Hydrogen bonding
2 Van der Waals forces
2.1 Keesom (permanent dipole) force
2.2 Debye (induced dipole) force
2.3 London dispersion force
3 Relative strength of forces
4 Quantum mechanical theories
5 See also
6 References
7 External links
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Dipole-dipole interactions are electrostatic interactions between permanent dipoles in molecules. These
interactions tend to align the molecules to increase attraction (reducing potential energy). An example of a
dipole-dipole interaction can be seen in hydrogen chloride (HCl): the positive end of a polar molecule will
attract the negative end of the other molecule and influence its position. Polar molecules have a net attraction
between them. Examples of polar molecules include hydrogen chloride (HCl) and chloroform (CHCl
3
).
Often molecules contain dipolar groups, but have no overall dipole moment. This occurs if there is symmetry
within the molecule that causes the dipoles to cancel each other out. This occurs in molecules such as
tetrachloromethane. Note that the dipole-dipole interaction between two individual atoms is usually zero, since
atoms rarely carry a permanent dipole. See atomic dipoles.
Ion-dipole and ion-induced dipole forces
Ion-dipole and ion-induced dipole forces are similar to dipole-dipole and 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.
An ion-dipole force consists of an ion and a polar molecule interacting. They align so that the positive and
negative groups are next to one another, allowing for maximum attraction.
An ion-induced dipole force consists of an ion and a non-polar molecule interacting. Like a dipole-induced
dipole force, the charge of the ion causes distortion of the electron cloud on the non-polar molecule.
[2]
Hydrogen bonding
A hydrogen bond is the attraction between the lone pair of an electronegative atom and a hydrogen atom that is
bonded to either nitrogen, oxygen, or fluorine.
[3]
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 interaction, produces interatomic distances shorter than the sum of van der Waals radius, and
usually involves a limited number of interaction partners, which can be interpreted as a kind of valence.
Intermolecular hydrogen bonding is responsible for the high boiling point of water (100 C) compared to the
other group 16 hydrides, which have no hydrogen bonds. Intramolecular hydrogen bonding is partly responsible
for the secondary, tertiary, and quaternary structures of proteins and nucleic acids. It also plays an important role
in the structure of polymers, both synthetic and natural.
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Keesom (permanent dipole) force
Keesom interactions (named after Willem Hendrik Keesom) are attractive interactions of dipoles that are
ensemble averaged over different rotational orientations of the dipoles. It is assumed that the molecules are
constantly rotating and never get locked into place. This is a good assumption, but at some point molecules do
get locked into place. The energy of a Keesom interaction depends on the inverse sixth power of the distance,
unlike the interaction energy of two spatially fixed dipoles, which depends on the inverse third power of the
distance. The Keesom interaction can only occur among molecules that possess permanent dipole moments aka
two polar molecules. Also Keesom interactions are very weak Van der Waals interactions and do not occur in
aqueous solutions that contain electrolytes. The angle averaged interaction is given by the following equation:
Where m =charge per length, =permitivity of free space, =dielectric constant of surrounding material, T
=temperature, =Boltzmann constant, and r =distance between molecules.
Debye (induced dipole) force
The induced dipole forces appear from the induction (also known as polarization), which is the attractive
interaction between a permanent multipole on one molecule with an induced (by the former di/multi-pole)
multipole on another.
[4][5][6][7]
This interaction is called the Debye force, named after Peter J .W. Debye.
One example of an induction-interaction between permanent dipole and induced dipole is the interaction
between HCl and Ar. In this system, Ar experiences a dipole as its electrons are attracted (to the H side of HCl)
or repelled (from the Cl side) by HCl.
[4][6]
The angle averaged interaction is given by the following equation.
Where =polarizability
This kind of interaction can be expected between any polar molecule and non-polar/symmetrical molecule. The
induction-interaction force is far weaker than dipole-dipole interaction, but stronger than the London dispersion
force.
London dispersion force
Otherwise known as quantum-induced instantaneous polarization or instantaneous dipole-induced dipole force,
the London dispersion force is caused by correlated movements of the electrons in interacting molecules.
Electrons that belong to different molecules start "fleeing" and avoiding each other at the short intermolecular
distances, which is frequently described as formation of "instantaneous dipoles" that attract each other.
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Bond type
Dissociation energy (kcal/mol)
[8]
Ionic Lattice Energy
250-4000
[9]
Covalent Bond Energy 30-260
Hydrogen Bonds 1-12 (about 5 in water)
DipoleDipole 0.52
London Dispersion Forces
<1 to 15 (estimated from the enthalpies of vaporization of hydrocarbons)
[10]
Note: this comparison is only approximate the actual relative strengths will vary depending on the molecules
involved. Ionic and covalent bonding will always be stronger than intermolecular forces in any given substance.
Intermolecular forces observed between atoms and molecules can be described phenomenologically as
occurring between permanent and instantaneous dipoles, as outlined above. 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 RayleighSchrdinger perturbation theory has been especially effective in this
regard. When applied to existing quantum chemistry methods, such a quantum mechanical explanation of
intermolecular interactions, this provides an array of approximate methods that can be used to analyze
intermolecular interactions.
Coomber's relationship
Force field
Hydrophobic effect
Intramolecular force
Molecular solid
Polymer
Quantum chemistry computer programs
Van der Waals force
Software for molecular mechanics modeling
Non-covalent interactions
Solvation
^ H. Margenau, N Kestner, Theory of intermolecular forces, International Series of Monographs in Natural
Philosophy, Pergamon Press
1.
^ Dr. Michael Blaber, 1996. Intermolecular Forces. http://www.mikeblaber.org/oldwine/chm1045/notes/Forces
/Intermol/Forces02.htm
2.
^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:
(2006) "hydrogen bond (http://goldbook.iupac.org/H02899.html)".
3.
^
a

b
Blustin PH, 1978. A Floating Gaussian Orbital calculation on argon hydrochloride (Ar HCl). Theoret. Chim.
Acta 47, 249257.
4.
^ Nannoolal Y, 2006. Development and critical evaluation of group contribution methods for the estimation of critical 5.
Intermolecular force - Wikipedia, the free encyclopedia http://en.wikipedia.org/wiki/Intermolecular_force
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properties, liquid vapour pressure and liquid viscosity of organic compounds. University of Kwazulu-Natal PhD
Thesis.
^
a

b
Roberts J K and Orr WJ C, 1938. Induced dipoles and the heat of adsorption of argon on ionic crystals. Trans.
Faraday Soc. 34, 13461349.
6.
^ Sapse AM, Rayez-Meaume MT, Rayez J C and Massa LJ , 1979. Ion-induced dipole H-n clusters. Nature 278,
332333.
7.
^ Organic Chemistry: Structure and Reactivity by Seyhan Ege, pp.3033, 67 8.
^ "Lattice Energies" (http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch7/lattice.html). Retrieved
2014-01-21.
9.
^ Majer, V. and Svoboda, V., Enthalpies of Vaporization of Organic Compounds, Blackwell Scientific Publications,
Oxford, 1985.}
10.
Software for calculation of intermolecular forces
Quantum 3.2 (http://www.q-pharm.com)
SAPT (http://www.physics.udel.edu/~szalewic/SAPT/): An ab initio quantumchemical package
intermolecular potential (http://scitation.aip.org/content/aip/journal/jcp/105/20/10.1063/1.472747)
Retrieved from "http://en.wikipedia.org/w/index.php?title=Intermolecular_force&oldid=603153985"
Categories: Intermolecular forces Chemical bonding
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