Density profiles of Ar adsorbed in slits of CO2: spontaneous symmetry breaking revisited.

Laboratorio TANDAR, Departamento de Física, Comisión Nacional de Energía Atómica, Av. del Libertador 8250, RA-1429 Buenos Aires, Argentina.
The Journal of Chemical Physics (Impact Factor: 3.12). 04/2008; 128(12):124702. DOI: 10.1063/1.2895747
Source: PubMed

ABSTRACT A recently reported symmetry breaking of density profiles of fluid argon confined by two parallel solid walls of carbon dioxide is studied. The calculations are performed in the framework of a nonlocal density functional theory. It is shown that the existence of such asymmetrical solutions is restricted to a special choice for the adsorption potential, where the attraction of the solid-fluid interaction is reduced by the introduction of a hard-wall repulsion. The behavior as a function of the slit's width is also discussed. All the results are placed in the context of the current knowledge on this matter.

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    ABSTRACT: Adsorption on single planar walls and filling of slits with identical planar walls are investigated in the frame of the density functional theory. In this sort of slits the external potential is symmetric with respect to its central plane. Calculations were carried out by applying both the canonical and grand canonical ensembles (CE and GCE, respectively). The behavior is analyzed by varying the strength of the adsorbate-substrate attraction, the temperature T, and the coverage Γℓ. Results obtained for physisorption of Xe on alkaline surfaces are reported in the present work. Prewetting (PW) lines and wetting temperatures, Tw, are determined from the analysis of adsorption on single walls. The filling of slits is analyzed for temperatures T > Tw. It is found that whenever for a given Xe-substrate combination the adsorption on a single wall exhibits a first-order wetting transition then asymmetric profiles that break the left-right symmetry of the external potential appear in the filling of an equivalent slit. These spontaneously symmetry breaking (SSB) solutions occur in a restricted range of Γℓ with a T-dependent width. In the case of closed slits analyzed in the CE scheme, the obtained asymmetric profiles exhibit lower Helmholtz free energies than the symmetric species and, therefore, could be stabilized in this geometry. For open slits, the GCE scheme yields all the symmetric and SSB states in the corresponding convex regimes of the free energy. It is shown that both the CE and the GCE frames yield three coexistent states, two symmetric and one asymmetric twofold degenerate. Both a PW line and the related SSB effect terminate at the same temperature. For rather strongly attractive surfaces reentrant SSB states are found at a fixed value of T.
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