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Issue 19, 2012
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Predicting cavity formation free energy: how far is the Gaussian approximation valid?

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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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Publication details

The article was received on 06 Jan 2012, accepted on 14 Mar 2012 and first published on 15 Mar 2012


Article type: Paper
DOI: 10.1039/C2CP00046F
Citation: Phys. Chem. Chem. Phys., 2012,14, 6996-7004
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    Predicting cavity formation free energy: how far is the Gaussian approximation valid?

    T. Head-Gordon, R. M. Lynden-Bell, J. R. Dowdle and P. J. Rossky, Phys. Chem. Chem. Phys., 2012, 14, 6996
    DOI: 10.1039/C2CP00046F

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