Induced-dipole interaction

The raie gas atoms reveal through their deviation from ideal gas behavior that electrostatics alone cannot account for all non-bonded interactions, because all multipole moments are zero. Therefore, no dipole-dipole or dipole-induced dipole interactions are possible. Van der Waals first described the forces that give rise to such deviations from the expected behavior. This type of interaction between two atoms can be formulated by a Lennaid-Jones [12-6] function Eq. (27)). 

Nonbonded interactions are the forces be tween atoms that aren t bonded to one another they may be either attractive or repulsive It often happens that the shape of a molecule may cause two atoms to be close in space even though they are sep arated from each other by many bonds Induced dipole/induced dipole interactions make van der Waals forces in alkanes weakly attractive at most distances but when two atoms are closer to each other than the sum of their van der Waals radii nuclear-nuclear and electron-electron repulsive forces between them dominate the fvan derwaais term The resulting destabilization is called van der Waals strain... 

Forces of Adsorption. Adsorption may be classified as chemisorption or physical adsorption, depending on the nature of the surface forces. In physical adsorption the forces are relatively weak, involving mainly van der Waals (induced dipole—induced dipole) interactions, supplemented in many cases by electrostatic contributions from field gradient—dipole or —quadmpole interactions. By contrast, in chemisorption there is significant electron transfer, equivalent to the formation of a chemical bond between the sorbate and the soHd surface. Such interactions are both stronger and more specific than the forces of physical adsorption and are obviously limited to monolayer coverage. The differences in the general features of physical and chemisorption systems (Table 1) can be understood on the basis of this difference in the nature of the surface forces. 

Attractive and Repulsive Forces. The force that causes small particles to stick together after colliding is van der Waals attraction. There are three van der Waals forces (/) Keesom-van der Waals, due to dipole—dipole interactions that have higher probabiUty of attractive orientations than nonattractive (2) Debye-van der Waals, due to dipole-induced dipole interactions (ie, uneven charge distribution is induced in a nonpolar material) and (J) London dispersion forces, which occur between two nonpolar substances. 

The induced counter-dipole can act in a similar manner to a permanent dipole and the electric forces between the two dipoles (permanent and induced) result in strong polar interactions. Typically, polarizable compounds are the aromatic hydrocarbons examples of their separation using induced dipole interactions to affect retention and selectivity will be given later. Dipole-induced dipole interaction is depicted in Figure 12. Just as dipole-dipole interactions occur coincidentally with dispersive interactions, so are dipole-induced dipole interactions accompanied by dispersive interactions. It follows that using an n-alkane stationary phase, aromatic... 

Figure 12. Polar Interactions Dipole-Induced Dipole Interactions...

Alternatively, using a polyethylene glycol stationary phase, aromatic hydrocarbons can also be retained and separated primarily by dipole-induced dipole interactions combined with some dispersive interactions. Molecules can exhibit multiple interactive properties. For example, phenyl ethanol possesses both a dipole as a result of the hydroxyl group and is polarizable due to the aromatic ring. Complex molecules such as biopolymers can contain many different interactive groups. 

There are three types of interactions that contribute to van der Waals forces. These are interactions between freely rotating permanent dipoles (Keesom interactions), dipole-induced dipole interaction (Debye interactions), and instantaneous dip le-induced dipole (London dispersion interactions), with the total van der Waals force arising from the sum. The total van der Waals interaction between materials arise from the sum of all three of these contributions. 

Both attractive forces and repulsive forces are included in van der Waals interactions. The attractive forces are due primarily to instantaneous dipole-induced dipole interactions that arise because of fluctuations in the electron charge distributions of adjacent nonbonded atoms. Individual van der Waals interactions are weak ones (with stabilization energies of 4.0 to 1.2 kj/mol), but many such interactions occur in a typical protein, and, by sheer force of numbers, they can represent a significant contribution to the stability of a protein. Peter Privalov and George Makhatadze have shown that, for pancreatic ribonuclease A, hen egg white lysozyme, horse heart cytochrome c, and sperm whale myoglobin, van der Waals interactions between tightly packed groups in the interior of the protein are a major contribution to protein stability. 

Where FCl is the solute gas-liquid partition coefficient, r is the tendency of the solvent to interact through k- and n-electron pairs (Lewis basicity), s the contribution from dipole-dipole and dipole-induced dipole interactions (in molecular solvents), a is the hydrogen bond basicity of the solvent, b is its hydrogen bond acidity and I is how well the solvent will separate members of a homologous series, with contributions from solvent cavity formation and dispersion interactions. 

In this equation, AG°CS is taken to be negligible for p- and y-cyclodextrin systems and to be constant, if there is any, for the a-cyclodextrin system. The AG W term is virtually independent of the kind of guest molecules, though it is dependent on the size of the cyclodextrin cavity. The AG dw term is divided into two terms, AG°,ec and AGs°ter, which correspond to polar (dipole-dipole or dipole-induced dipole) interactions and London dispersion forces, respectively. The former is mainly governed by the electronic factor, the latter by the steric factor, of a guest molecule. Thus, Eq. 2 is converted to Eq. 3 for the complexation of a particular cyclodextrin with a homogeneous series of guest molecules ... 

Also known as the induced-dipole-induced-dipole interaction. 

Closely related to the London interaction is the dipole-induced-dipole interaction, in which a polar molecule interacts with a nonpolar molecule (for example, when oxygen dissolves in water). Like the London interaction, the dipole—induced-dipole interaction arises from the ability of one molecule to induce a dipole moment in the other. However, in this case, the molecule that induces the dipole moment has a permanent dipole moment. The potential energy of the interaction is... 

Once again, the potential energy is inversely proportional to the sixth power of the separation. Notice that the potential energies of the dipole-dipole interaction of rotating polar molecules in the gas phase, the London interaction, and the dipole-induced-dipole interaction all have the form... 

The London interaction arises from the attraction between instantaneous electric dipoles on neighboring molecules and acts between all types of molecules its strength increases with the number of electrons and occurs in addition to any dipole-dipole interactions. Polar molecules also attract nonpolar molecules by weak dipole-induced-dipole interactions. 

In Table III we compare for several reactions the experimental rate constants with rate constants calculated on the basis of ion-induced dipole interactions only from the relation (4) ... 

The first two terms C/cou and C/poL correspond to the empirical energy of ion-dipole and ion-induced dipole interactions, being given by... 

The dipole-induced dipole interactions are summed over all atoms and expressed as the Hamaker constant (A). The total molecular potential, Um, for two perfectly spherical particles with diameters d and d2 is ... 

The inducing field responsible for the energy of the induced dipoles, Umd, has contributions from three terms the permanent or static field, Ustat, the induced dipole-induced dipole interaction, Udip, and the polarization energy, Upou... 

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