Liquid-vapor interface of a polydisperse fluid

Details Liquid-vapor interface of a polydisperse fluid Liquid-vapor interface of a polydisperse fluid

2005-02-24

arxiv.org/abs/cond-mat/0502573v1

Physics

Condensed Matter

Soft Condensed Matter

9 pages, 10 Figs

Scientific paper

10.1103/PhysRevE.71.066126

We report a Grand Canonical Monte Carlo simulation study of the liquid-vapor interface of a model fluid exhibiting polydispersity in terms of the particle size $\sigma$. The bulk density distribution, $\rho^0(\sigma)$, of the system is controlled by the imposed chemical potential distribution $\mu(\sigma)$. We choose the latter such that $\rho^0(\sigma)$ assumes a Schulz form with associated degree of polydispersity $\approx 14%$. By introducing a smooth attractive wall, a planar liquid-vapor interface is formed for bulk state points within the region of liquid-vapor coexistence. Owing to fractionation, the pure liquid phase is enriched in large particles, with respect to the coexisting vapor. We investigate how the spatial non-uniformity of the density near the liquid-vapor interface affects the evolution of the local distribution of particle sizes between the limiting pure phase forms. We find (as previously predicted by density functional theory, Bellier-Castella {\em et al}, Phys. Rev. {\bf E65}, 021503 (2002)) a segregation of smaller particles to the interface. The magnitude of this effect is quantified for various $\sigma$ via measurements of the relative adsorption. Additionally, we consider the utility of various estimators for the interfacial width and highlight the difficulties of isolating the intrinsic contribution of polydispersity to this width.

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