Modeling hydrophobic solvation of nonspherical systems: Comparison of use of molecular surface area with accessible surface area

✍ Scribed by Hermann, Robert B.

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 237 KB
• Volume: 18
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(19970115)18:1<115::aid-jcc11>3.0.co;2-l

✦ Synopsis

It is shown that the molecular surface and the accessible surface lead to exactly the same results when calculating solvation free energies and transfer free energies, from methods using the surface tension as a parameter if the exact geometric curvature is used with the accessible surface. However, the use of the exact curvature is not necessarily the best approach chemically. Other modifications, including an approximate curvature improves the approach. Such modifications are difficult to include in methods in which the molecular surface rather than the accessible surface is used to calculate solvent effects. A modification of a Gaussian curvature term is necessary if dissociation is to be accounted for properly. The inclusion of a Gaussian curvature term, in addition to the usual mean curvature term, reconciles the difference in magnitude of the microscopic and macroscopic surface tension in the case of the accessible surface area.