Analysis of the Henderson–Abraham–Barker equation in the case of a polar liquid near a neutral hard wall

Badiali, J. P.; Russier, V.; Holovko, M. E.
November 1993
Journal of Chemical Physics;11/15/1993, Vol. 99 Issue 10, p8051
Academic Journal
The physical content of the wall–particle direct correlation function cw(1), defined from the Ornstein–Zernike equation in the framework of the Henderson–Abraham–Barker approach, is analyzed in the case of a dipolar-hard-sphere fluid near a pure and dielectric neutral wall. The exact asymptotic behavior of cw(1) is established and we show that it is not related to simple physical concepts as, e.g., the image potential. We show that the exact Henderson–Abraham–Barker equation introduces some bridge diagrams which are more simple graphs in another approach. Due to this fact, at least for systems with long range interactions, it is misleading to use the usual closures of the theory of homogeneous liquids for cw(1). In the case of a dielectric wall, we emphasize that the diagrammatic structure of cw(1) requires the introduction of a three-body Mayer function. The dipolar-hard-sphere liquid is a good candidate for analyzing cw(1) because some exact results are known and related to simple electrostatic effects; however, the present results are not restricted to this system.


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