Molecular theory and the effects of solute attractive forces on hydrophobic interactions

Abstract

The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. We present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions \emph{diminishes} the strength of hydrophobic bonds. For the Ar-Ar rdfs considered pointwise, the numerical results for the effects of solute attractive forces on hydrophobic interactions are of opposite sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasi-chemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar-Ar rdfs permit evaluation of osmotic second virial coefficients $B_2$. Those $B_2$ also show that incorporation of attractive interactions leads to more positive (repulsive) values. With attractive interactions in play, $B_2$ can change from positive to negative values with increasing temperatures. This is consistent with the historical work of Watanabe, \emph{et al.,} that $B_2 \approx 0$ for intermediate cases. In all cases here, $B_2$ becomes more attractive with increasing temperature.