Response to "Comment on 'A simple molecular thermodynamic theory of hydrophobic hydration' " [J. Chem. Phys. 119, 10448 (2003)]

In this response, we present a generalized condition for the observation of entropy convergence behavior for hydrophobic hydration. Applied within the context of our previously developed partition function for aqueous mixtures with nonpolar solutes, it is shown that entropy convergence is observed at a unique temperature when the thermal expansion coefficient of liquid water satisfies specific criterion. Hydrogen-bonding is essential and van der Waals-type fluids never display this phenomenon. Comparing these results to the discussion of Graziano who contends transient hydrogen-bond fluctuations in water dominate entropy convergence, we find that both van der Waals and hydrogen-bonding contributions are significant within the context of our model. In addition, it is pointed out that molecular-level conclusions drawn from a mean-field model should be made with caution.