  Recent studies on the solvation of atomistic and nanoscale solutes indicate
that a strong coupling exists between the hydrophobic, dispersion, and
electrostatic contributions to the solvation free energy, a facet not
considered in current implicit solvent models. We suggest a theoretical
formalism which accounts for coupling by minimizing the Gibbs free energy of
the solvent with respect to a solvent volume exclusion function. The resulting
differential equation is similar to the Laplace-Young equation for the
geometrical description of capillary interfaces, but is extended to microscopic
scales by explicitly considering curvature corrections as well as dispersion
and electrostatic contributions. Unlike existing implicit solvent approaches,
the solvent accessible surface is an output of our model. The presented
formalism is illustrated on spherically or cylindrically symmetrical systems of
neutral or charged solutes on different length scales. The results are in
agreement with computer simulations and, most importantly, demonstrate that our
method captures the strong sensitivity of solvent expulsion and dewetting to
the particular form of the solvent-solute interactions.
