Intermolecular forces (forces between two molecules) are weak compared to the intramolecular forces (forces keeping a molecule

together). For example, the covalent bond present within HCl molecules is much stronger than the forces present between the neighbouring molecules. These forces exist between molecules when they are sufficiently close to each other. The forces consist of four types: 1. 2. 3. 4. Dipoledipole forces Iondipole forces Dipole-induced dipole force or Debye forces Instantaneous dipole-induced dipole forces or London dispersion forces.

London dispersion forces (LDF, also known as dispersion forces, London forces, instantaneous dipoleinduced dipole forces) is a type of force acting between atoms and molecules. They are part of the van der Waals forces. The LDF is named after the German-American physicist Fritz London. The LDF is a weak intermolecular force arising from quantum induced instantaneous polarization multipoles in molecules. They can therefore act between molecules without permanent multipole moments. London forces are exhibited by nonpolar molecules because of the correlated movements of the electrons in interacting molecules. Because the electrons from different molecules start "feeling" and avoiding each other, electron density in a molecule becomes redistributed in proximity to another molecule, (see quantum mechanical theory of dispersion forces). This is frequently described as formation of "instantaneous dipoles" that attract each other. London forces are present between all chemical groups and usually represent the main part of the total interaction force in condensed matter, even though they are generally weaker than ionic bonds and hydrogen bonds.This is the only attractive intermolecular force present between neutral atoms (e.g., a noble gas). Without London forces, there would be no attractive force between noble gas atoms, and they wouldn't exist in liquid form.London forces become stronger as the atom or molecule in question becomes larger. This is due to the increased polarizability of molecules with larger, more dispersed electron clouds. This trend is exemplified by the halogens (from smallest to largest: F2, Cl2, Br2, I2). Fluorine and chlorine are gases at room temperature, bromine is a liquid, and iodine is a solid. The London forces also become stronger with larger amounts of surface contact. Greater surface area means closer interaction between different molecules. Quantum mechanical theory of dispersion forces The first explanation of the attraction between noble gas atoms was given by Fritz London in 1930. He used a quantum mechanical theory based on second-order perturbation theory. The perturbation is the Coulomb interaction V between the electrons and nuclei of the two monomers (atoms or molecules) that constitute the dimer. The second-order perturbation expression of the interaction energy contains a sum over states. The states appearing in this sum are simple products of the stimulated electronic states of the monomers. Thus, no intermolecular antisymmetrization of the electronic states is included and the Pauli exclusion principle is only partially satisfied.

London developed the method perturbation V in a Taylor series in , where R is the distance between the nuclear centers of mass of the monomers.This Taylor expansion is known as the multipole expansion of V because the terms in this series can be regarded as energies of two interacting multipoles, one on each monomer. Substitution of the multipole-expanded form of V into the second-order energy yields an expression that resembles somewhat an expression describing the interaction between instantaneous multipoles (see the qualitative description above). Additionally an approximation, named after Albrecht Unsld, must be introduced in order to obtain a description of London dispersion in terms of dipole polarizabilities and ionization potentials.

In this manner the following approximation is obtained for the dispersion interaction between two atoms A and B. Here and are the dipole polarizabilities of the respective atoms. The quantities IA and IB are the first ionization potentials of the atoms and R is the intermolecular distance.

Note that this final London equation does not contain instantaneous dipoles (see molecular dipoles). The "explanation" of the dispersion force as the interaction between two such dipoles was [5] invented after London gave the proper quantum mechanical theory. See the authoritative work for a criticism of the instantaneous dipole model and for a modern and thorough exposition of the theory of intermolecular forces. The London theory has much similarity to the quantum mechanical theory of light dispersion, which is why London coined the phrase "dispersion effect". Relative magnitude-Dispersion forces are usually dominant of the three van der Waals forces (orientation, induction, dispersion) between atoms and molecules, with the exception for molecules that are small and highly polar, like of water. The following contribution of the dispersion to the total intermolecular interaction energy has been given: Contribution of the dispersion to the total intermolecular interaction energy Molecule pair % of the total energy of interaction Ne-Ne 100 CH4-CH4 100 HCl-HCl 86 HBr-HBr 96 HI-HI 99 CH3Cl-CH3Cl 68 NH3-NH3 57 H2O-H2O 24 HCl-HI 96 H2O-CH4 87

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 (Ref 4-7). This interaction is called Debye force after Peter J.W. Debye. The example of an induction-interaction between permanent dipole and induced dipole is HCl and Ar. In this system, Ar experiences a dipole as its electrons are attracted (to H side) or repelled (from Cl side) by HCl (Ref 4, 6). This kind of interaction can be expected between any polar molecule and non-polar/symmetrical molecule. The induction-interaction force is far weaker than dipoledipole interaction, however stronger than London force.They induce their properties in another atom Dipoledipole interactions Dipoledipole interactions are electrostatic interactions of permanent dipoles in molecules. These interactions tend to align the molecules to increase the attraction (reducing potential energy). An example of a dipoledipole 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 cause them to be arranged in a specific arrangement. Polar molecules have a net attraction between them. For example HCl and chloroform (CHCl3)

Keesom interactions (named after Willem Hendrik Keesom) are attractive interactions of dipoles that are Boltzmann-averaged over different rotational orientations of the dipoles. 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.

Often, molecules have dipolar groups within them, but have no overall dipole moment. This occurs if there is symmetry within the molecule, causing the dipoles to cancel each other out. This occurs in molecules such as tetrachloromethane. Note that the dipoledipole interaction between two atoms is usually zero, because atoms rarely carry a permanent dipole. See atomic dipoles. A hydrogen bond is the attractive interaction of a hydrogen atom with an electronegative atom, such as nitrogen, oxygen or fluorine, that comes from another molecule or chemical group. The hydrogen must be covalently bonded to another electronegative atom to create the bond. These bonds can occur between molecules (intermolecularly), or within different parts of a single [2] molecule (intramolecularly). The hydrogen bond (5 to 30 kJ/mole) is stronger than a van der Waals interaction, but weaker than covalent or ionic bonds. This type of bond occurs in both inorganic molecules such as water and organic molecules such as DNA. Intermolecular hydrogen bonding is responsible for the high boiling point of water (100 C) compared to the other group 16 hydrides that 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. A task group formed by IUPAC has come up with a modern definition of hydrogen bonding in 2011. This new definition can be seen in the IUPAC journal Pure and Applied Chemistry. A detailed [4] technical report provides the rationale behind the new definition. Bonding A hydrogen atom attached to a relatively electronegative atom is a hydrogen bond donor. This electronegative atom is usually fluorine, oxygen, or nitrogen. An electronegative atom such as fluorine, oxygen, or nitrogen is a hydrogen bond acceptor, regardless of whether it is bonded to a hydrogen atom or not. An example of a hydrogen bond donor is ethanol, which has a hydrogen bonded to oxygen; an example of a hydrogen bond acceptor which does not have a hydrogen atom bonded to it is the oxygen atom on diethyl ether.
[5] [3]

Examples of hydrogen bond donating (donors) and hydrogen bond accepting groups (acceptors)

Carboxylic acids often form dimers in vapor phase. A hydrogen attached to carbon can also participate in hydrogen bonding when the carbon atom is bound to electronegative atoms, as is the case in chloroform, CHCl3. The electronegative atom attracts the electron cloud from around the hydrogen nucleus and, by decentralizing the cloud, leaves the atom with a positive partial charge. Because of the small size of hydrogen relative to other atoms and molecules, the resulting charge, though only partial, represents a large charge density. A hydrogen bond results when this strong positive charge density attracts a lone pair of electrons on another heteroatom, which becomes the hydrogen-bond Acceptor.

The hydrogen bond is often described as an electrostatic dipole-dipole interaction. However, it also has some features of covalent bonding: it is directional and strong, produces interatomic distances shorter than sum of van der Waals radii, and usually involves a limited number of interaction partners, which can be interpreted as a type of valence. These covalent features are more substantial when acceptors bind hydrogens from more electronegative donors. The partially covalent nature of a hydrogen bond raises the following questions: "To which molecule or atom does the hydrogen nucleus belong?" and "Which should be labeled 'donor' and which 'acceptor'?" Usually, this is simple to determine on the basis of interatomic distances in the XH Y system: XH distance is typically 110 pm, whereas H Y distance is 160 to 200 pm. Liquids that display hydrogen bonding are called associated liquids. Hydrogen bonds can vary in strength from very weak (12 kJ mol ) to extremely strong (161.5 kJ mol in the ion HF [6][7] 2). Typical enthalpies in vapor include:
1 1

FH :F (161.5 kJ/mol or 38.6 kcal/mol) OH :N (29 kJ/mol or 6.9 kcal/mol) OH :O (21 kJ/mol or 5.0 kcal/mol) NH :N (13 kJ/mol or 3.1 kcal/mol) NH :O (8 kJ/mol or 1.9 kcal/mol) HOH :OH+ 3 (18 kJ/molor 4.3 kcal/mol; data obtained using molecular dynamics as detailed in the reference and should be compared to 7.9 kJ/mol for bulk waters, obtained using the same molecular dynamics.)

The length of hydrogen bonds depends on bond strength, temperature, and pressure. The bond strength itself is dependent on temperature, pressure, bond angle, and environment (usually characterized by local dielectric constant). The typical length of a hydrogen bond in water is 197 pm. The ideal bond angle depends on the nature of the hydrogen bond donor. The following [9] hydrogen bond angles between a hydrofluoric acid donor and various acceptors have been determined experimentally: Acceptor donor HCN HF H2CO HF H2O HF H2S HF SO2 HF

VSEPR symmetry linear trigonal planar pyramidal pyramidal trigonal

Angle () 180 110 46 89 142