Dispersion Force Distribution

The most important second-order forces are dispersion forces. London [3, 31, 32] showed that they are caused by a correlation of tlie electron distribution in one molecule with tliat in the other, and pointed out that the... 

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. 

Dispersion force (Section 2.13) A noncovalent interaction between molecules that arises because of constantly changing electron distributions within the molecules. 

The effect of molecular interactions on the distribution coefficient of a solute has already been mentioned in Chapter 1. Molecular interactions are the direct effect of intermolecular forces between the solute and solvent molecules and the nature of these molecular forces will now be discussed in some detail. There are basically four types of molecular forces that can control the distribution coefficient of a solute between two phases. They are chemical forces, ionic forces, polar forces and dispersive forces. Hydrogen bonding is another type of molecular force that has been proposed, but for simplicity in this discussion, hydrogen bonding will be considered as the result of very strong polar forces. These four types of molecular forces that can occur between the solute and the two phases are those that the analyst must modify by choice of the phase system to achieve the necessary separation. Consequently, each type of molecular force enjoins some discussion. 

The discussion thus far has focused on the forces between an array of atoms connected together through covalent bonds and their angles. Important interactions occur between atoms not directly bonded together. The theoretical explanation for attractive and repulsive forces for nonbonded atoms i and j is based on electron distributions. The motion of electrons about a nucleus creates instantaneous dipoles. The instantaneous dipoles on atom i induce dipoles of opposite polarity on atom j. The interactions between the instantaneous dipole on atom i with the induced instantaneous dipole on atom j of the two electron clouds of nonbonded atoms are responsible for attractive interactions. The attractive interactions are know as London Dispersion forces,70 which are related to r 6, where r is the distance between nonbonded atoms i and j. As the two electron clouds of nonbonded atoms i and j approach one another, they start to overlap. There is a point where electron-electron and nuclear-nuclear repulsion of like charges overwhelms the London Dispersion forces.33 The repulsive... 

Dispersion forces. These are weak attractions caused by instantaneous fluctuation of the electron distribution in molecules and even atoms. They were first posed by Fritz London whose focus was on helium liquefaction. Such London forces fall off with the sixth power of the distance of separation. Any individual fluctuation creates a +/— local charge and that instantaneous dipole can interact with other such instantaneous dipoles nearby. The important... 

The dispersive force arises due to the intermolecular electron correlation between the solute and the solvent. Further, it is also important to include the changes in intramolecular and intermolecular solvent electron correlation upon insertion of the solute in the solvent continuum. Further, electron correlation affects the structure of the solute and its charge distribution. Hence, the wave function obtained from the calculation with electron correlation provides a more accurate description of reaction field. 

Fowkes and co-workers also clearly demonstrated that the physical Interaction of polymers with neighboring molecules was determined by only two kinds of interactions London dispersion forces and Lewis acid-base interactions (21) Calculations based on this concept were shown to correct many of the problems inherent in the solubility approach. They were also able to use the concept to study the distribution of molar heats of absorption of various polymers onto ferric oxides, and thereby more accurately described the requirements for adequate adhesion to steel substrates (21) In the symposium on which this book is based, Fowkes summarized work showing that the polar Interactions between polymers and metal surfaces that are... 

The stability of the molecular conformation of organic solids Is determined by the nature and distribution within the molecular network of both covalent crosslinks and the various non-covalent Interactions. The latter Include localized (e.g. hydrogen bonds) and non-locallzed electrostatic Interactions and the short-range non-polar Interactions between molecular units due to the ubiquitous and weak van der Waals Induction and dispersion forces (7 ). 

Lipophilicity is a molecular property experimentally determined as the logarithm of the partition coefficient (log P) of a solute between two non-miscible solvent phases, typically n-octanol and water. An experimental log P is valid for only a single chemical species, while a mixture of chemical species is defined by a distribution, log D. Because log P is a ratio of two concentrations at saturation, it is essentially the net result of all intermolecular forces between a solute and the two phases into which it partitions (1) and is generally pH-dependent. According to Testa et al. (1) lipophilicity can be represented (Fig. 1) as the difference between the hydrophobicity, which accounts for hydrophobic interactions, and dispersion forces and polarity, which account for hydrogen bonds, orientation, and induction forces ... 

Like the Coulombic forces, the van der Waals interactions decrease less rapidly with increasing distance than the repulsive forces. They include interactions that arise from the dipole moments induced by nearby charges and permanent dipoles, as well as interactions between instantaneous dipole moments, referred to as dispersion forces (Israelachvili 1992). Instantaneous dipole moments can be thought of as arising from the motions of the electrons. Even though the electron probability distribution of a spherical atom has its center of gravity at the nuclear position, at any very short instance the electron positions will generally not be centered on the nucleus. 

Molecules that have no permanent dipole still have their electrons in movement. Although the time-averaged distribution of electrons is symmetrical, at any instant the electrons are not uniformly distributed, so the molecule has a small instantaneous dipole, p. This instantaneous dipole can polarize electrons in a neighboring molecule, giving a small dipole in the molecules. This is the dispersion attraction responsible for molecules sticking together. These dispersions forces are the weakest of all inter-... 

Dispersion forces57 , which result from temporary variations in the distribution of electron density in atoms, can account for up to 90 per cent58 of the adhesion forces between non-polar polymers and metal substrates (bond energy 0.5-5 Kcal/ mole)50 . However, for the adhesion of epoxy resins and other polar polymers to metals, dispersion forces are of secondary importance when compared to the electromagnetic and mechanical interactions discussed above. 

Figure 3.1 Illustration of the various molecular interactions arising from uneven electron distributions (a) dispersive forces, (b) dipole-induced dipole forces, (c) dipole-dipole forces, (d) electron acceptor-electron donor forces.

---