Title | INTERACTION FREE-ENERGY BETWEEN PLANAR WALLS IN DENSE FLUIDS - AN ORNSTEIN-ZERNIKE APPROACH WITH RESULTS FOR HARD-SPHERE, LENNARD-JONES, AND DIPOLAR SYSTEMS |
Publication Type | Journal Article |
Year of Publication | 1991 |
Authors | Attard, P, Berard, DR, Ursenbach, CP, Patey, GN |
Journal | Physical Review A |
Volume | 44 |
Pagination | 8224-8234 |
Date Published | Dec |
Type of Article | Article |
ISBN Number | 1050-2947 |
Keywords | APPROXIMATION, ELECTRICAL DOUBLE-LAYERS, ELECTROLYTES, equation, HYPERNETTED-CHAIN, INHOMOGENEOUS FLUIDS, INVARIANT EXPANSION, MODEL, MONTE-CARLO, SURFACES |
Abstract | The interaction free energy per unit area between planar walls is given as a convolution of wall-solvent pair-correlation functions. This result, derived from the large radius limit of the macrosphere-solvent Ornstein-Zernike equations, and from the hypernetted-chain closure, provides a statistical-mechanical basis for the Derjaguin approximation, and is both generally applicable and computationally tractable. It is found that the interaction between hard walls in a hard-sphere fluid is oscillatory, and in good agreement with simulations. The van der Waals attraction emerges from asymptotic analyses of Lennard-Jones and dipolar fluids, and the full expression allows calculation of this quantity down to molecular separations. This is demonstrated by numerical results for dipolar fluids. |
URL | <Go to ISI>://A1991GW60400049 |
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