Induction dispersion

The idea of solvent polarity refers not to bonds, nor to molecules, but to the solvent as an assembly of molecules. Qualitatively, polar solvents promote the separation of solute moieties with unlike charges and they make it possible for solute moieties with like charges to approach each other more closely. Polarity affects the solvent s overall solvation capability (solvation power) for solutes. The polarity depends on the action of all possible, nonspecific and specific, intermolecular interactions between solute ions or molecules and solvent molecules. It covers electrostatic, directional, inductive, dispersion, and charge-transfer forces, as well as hydrogen-bonding forces, but excludes interactions leading to definite chemical alterations of the ions or molecules of the solute. 

The characterization of a solvent by means of its polarity is an unsolved problem since the polarity itself has, until now, not been precisely defined. Polarity can be understood to mean (a) the permanent dipole moment of a compound, (b) its dielectric constant, or (c) the sum of all those molecular properties responsible for all the interaction forces between solvent and solute molecules (e.g., Coulombic, directional, inductive, dispersion, hydrogen bonding, and EPD/EPA interaction forces) (Kovats, 1968). The important thing concerning the so-called polarity of a solvent is its overall solvation ability. This in turn depends on the sum of all-specific as well as nonspecific interactions between solvent and solute. 

Compounds Approximation Electrostatic Components Inductive Dispersion Repulsion Total... 

In this section we will review the symmetry-adapted perturbation theory of pairwise nonadditive interactions in trimers. This theory was formulated in Ref. (302). We will show that pure three-body polarization and exchange components can be explicitly separated out and that the three-body polarization contributions through the third-order of perturbation theory naturally separate into terms describing the pure induction, mixed induction-dispersion, and pure dispersion interactions. 

The induction-dispersion contribution, in turn, can be interpreted as the energy of the (second-order) dispersion interaction of the monomer X with the monomer Y deformed by the electrostatic field of the monomer Z (note that we have six such contributions). In particular, when X=A, Y=B, and Z=C the corresponding induction-dispersion contribution in terms of response functions is given by,... 

We wish to end this section by saying that similarly as in the two-body case, nonadditive induction, induction-dispersion, and dispersion terms have well defined asymptotic behaviors from the multipole expansions of the intermolecular interaction operators. For instance, the leading term in the multipole expansion of the three-body dispersion energy for three atoms in a triangular geometry is given by the famous Axilrod-Teller-Muto formula311,312,... 

In Eq. (1-220) RXY denotes the distance between the atoms X and Y, while dA, dB, and l)c are the inner angles in the triangle ABC. General, open-ended formulas for the multipole-expanded induction, induction-dispersion, and dispersion energies through the third order are reported in Ref. (302). Specific applications to the Ar2-HF trimer and comparison of the multipole-expanded and nonexpanded results is given in Ref. (313). 

As the understanding of chemical bonding was advanced through such concepts as covalent and ionic bond, lone electron pairs etc., the theory of intermolecular forces also attempted to break down the interaction energy into a few simple and physically sensible concepts. To describe the nonrelativistic intermolecular interactions it is sufficient to express them in terms of the aforementioned four fundamental components electrostatic, induction, dispersion and exchange energies. 

A comparison of higher order effects also proves instructive A HF has a significant contribution from the induction-dispersion coupling, whereas A HCl, from the exchange-dispersion effect. In conclusion, the three-body effect in these systems represents a somewhat different blend, with the induction-type components being much more important for Ar2HF. 

The interaction of the carbon dioxide molecule with the sieve includes electrostatic, induction, dispersion, and repulsion contributions. The CO2 molecule was assumed to be capable of free rotation, so that the directional interactions could be averaged over all orientations using a Boltzmann weighting factor (JJ) this causes the electrostatic ion-quadrupole interaction to depend on the temperature. Mean values were used for the polarizability (a), the diamagnetic susceptibility (x), and the equilibrium radius of the CO2 molecule. Using vector summation for the total electric field at the CO2 molecule, the total potential, c(r), at a given position r is given by ... 

Induction, Dispersion Multipole Interactions, Penetration Effects... 

For the evaluation of the averaged induction-dispersion interaction we here... 

Torheyden, M. and Jansen, G. (2006) A new potential energy surface for the water dimer obtained from separate fits of ab-initio electrostatic, induction, dispersion and exchange energy contributions. Mol. Phys., 104, 2101-2138. 

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