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Predicting cavity formation free energy: how far is the Gaussian approximation valid?
T. Head-Gordon,R. M. Lynden-Bell,John R. Dowdle,P. J. Rossky
Physical Chemistry Chemical Physics Pub Date : 03/15/2012 00:00:00 , DOI:10.1039/C2CP00046F
Abstract

We examine the range of validity of the Gaussian model for various water-like liquids whose intermolecular potentials differ from SPC/E water, to provide insight into the temperature dependence of the hydrophobic effect for small hard sphere solutes. We find that low compressibility liquids that have more close-packed network structures show much larger deviations from Gaussian fluctuations for low or zero occupancies relative to more compressible fluids with more open networks. Water appears to be a unique molecular fluid in possessing equilibrium density fluctuations that are faithfully described by the Gaussian theory. We ascribe this success to the fact, shown here, that the orientational correlations near a small hard sphere solute involve remarkably little reorganization from the bulk, which is a consequence of water's low solvent reorganization enthalpy and entropy.

Graphical abstract: Predicting cavity formation free energy: how far is the Gaussian approximation valid?
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