Physics – Condensed Matter – Soft Condensed Matter
Scientific paper
2004-10-07
Physics
Condensed Matter
Soft Condensed Matter
17 pages, 3 figures; accepted for publication in J. Chem. Phys
Scientific paper
10.1063/1.1819316
We investigate the solvation of a hard spherical cavity, of radius $R$, immersed in a fluid for which the interparticle forces are short ranged. For thermodynamic states lying close to the liquid binodal, where the chemical potential deviation $\delta \mu\equiv \mu - \mu_{co}(T)$ is very small and positive, complete wetting by gas (drying) occurs and two regimes of interfacial behavior can be identified. These are characterized by the length scale $R_c=2 \gamma_{gl}^\infty/(\Delta \rho \delta \mu)$, where $\gamma_{gl}^\infty$ is the planar gas-liquid surface tension and $\Delta \rho$ is the difference in coexisting densities at temperature $T$. For $R>R_c$, the interfacial free energy and the density profile of the fluid near the hard wall can be expanded in powers of the curvature $R^{-1}$, in keeping with the analysis of Stillinger and Cotter, J. Chem. Phys. {\bf 55}, 3449 (1971). In the other regime, $R
Evans Robert
Henderson John R.
Roth Raphael
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