Faraday Symposia of the Chemical Society
Faraday Symposia of the Chemical Society was published from 1972 - 1984. In 1985 it continued as Faraday Discussions.
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Paper
Faraday Symp. Chem. Soc., 1982, 17, 55 - 67, DOI: 10.1039/FS9821700055
Thermodynamics of cavity formation in water. A molecular dynamics study
Johan P. M. Postma, Herman J. C. Berendsen and Jan R. Haak
Thermodynamic quantities related to the solvation of hydrophobic solutes in water can be approximated by the application of scaled-particle theory. The crucial quantity is the Gibbs free energy of cavity formation. A series of six molecular-dynamics simulations of water including repulsive cavities of various sizes has been carried out. Using perturbation statistical mechanics, the free energy has been derived as a function of cavity radius up to 0.32 nm (0.32 nm approach of water oxygens to the cavity centre). The free energy agrees well with predictions from scaled-particle theory and the experimental surface tension is predicted to within 5%. The radial distribution of water molecules with respect to the cavity has been determined for five cavity sizes; for one size (radius of approach of water oxygens of 0.3 nm) the orientational distribution and the residence-time distribution in the hydration shells has been determined.
