Differences between pair and bulk hydrophobic interactions

It is now well known that the pair interaction between two hydrocarbon molecules in water has distinctly different properties from the bulk hydrophobic interaction familiar to the biochemist, which is modeled by the transfer of a hydrocarbon from aqueous solutions to pure liquid hydrocarbon. We consider experimental data for pair interactions, which have been fitted by a simple empirical potential function, and point out some of their properties. (i) Surface free energy and cosphere overlap models, of the type considered until now, cannot reproduce correctly both the pair and bulk hydrophobic interactions. (ii) Pair interactions though still attractive are strikingly weaker in aqueous solution than in the gas phase, in contrast to the usual view of hydrophobic interactions. (iii) For pair interactions in water, the solvent-separated configuration is less important than the contact configuration if the hydrocarbon has more than two carbon atoms.