Dispersion effect, intramolecular

In 1963 Schaefer and co-workers (87) introduced an intramolecular dispersion effect in analogy to corresponding intermolecular effects exerted, for example, by halogenated solvents. This concept bears a close resemblance to the SEF contribution as expressed by eq. [10]. 

Calculations of a similar nature have demonstrated that replacement of both hydrogens of water, yielding dimethyl ether, also has only a minor effect upon the nature of the H-bond in the water dimer. With their polarized basis set, and with inclusion of corrections for BSSE, dispersion, and intramolecular correlation effects, these authors found the first methyl substitution raises the binding energy by 0.5 kcal/mol and the second by 0.6. The authors cautioned that an unpolarized basis set would fail to pick up these small effects, which they attribute to Coulomb and dispersion components of the interaction. 

The DFT-D method does not only work for molecular complexes and intramolecular dispersion effects but is rather general, and Sauer and coworkers extended this correction to periodic systems (Kerber et al. 2008). 

Site isolation effects catalytically active centres such as metal complexes can be dispersed over the zeolite matrix. In this way, reaction between adjacent metal centres can be impeded for steric reasons (7). In other well-documented cases, intramolecular reactions are preferred over intermolecular reactions due to the spatial isolation of molecules adsorbed in low concentrations (8)... 

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