Attenuation of London Dispersion in Dichloromethane Solutions

London dispersion constitutes one
of the fundamental interaction
forces between atoms and between molecules. While modern computational
methods have been developed to describe the strength of dispersive
interactions in the gas phase properly, the importance of inter- and
intramolecular dispersion in solution remains yet to be fully understood
because experimental data are still sparse in that regard. We herein
report a detailed experimental and computational study of the contribution
of London dispersion to the bond dissociation of proton-bound dimers,
both in the gas phase and in dichloromethane solution, showing that
attenuation of inter- and intramolecular dispersive interaction by
solvent is large (about 70% in dichloromethane), but not complete,
and that current state-of-the-art implicit solvent models employed
in quantum-mechanical computational studies treat London dispersion
poorly, at least for this model system.