Article

# 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

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**ABSTRACT:**We propose a numerical scheme based on the Chebyshev pseudo-spectral collocation method for solving the integral and integro-differential equations of the density-functional theory and its dynamic extension. We demonstrate the exponential convergence of our scheme, which typically requires much fewer discretization points to achieve the same accuracy compared to conventional methods. This discretization scheme can also incorporate the asymptotic behavior of the density, which can be of interest in the investigation of open systems. Our scheme is complemented with a numerical continuation algorithm and an appropriate time stepping algorithm, thus constituting a complete tool for an efficient and accurate calculation of phase diagrams and dynamic phenomena. To illustrate the numerical methodology, we consider an argon-like fluid adsorbed on a Lennard-Jones planar wall. First, we obtain a set of phase diagrams corresponding to the equilibrium adsorption and compare our results obtained from different approximations to the hard sphere part of the free energy functional. Using principles from the theory of sub-critical dynamic phase field models, we formulate the time-dependent equations which describe the evolution of the adsorbed film. Through dynamic considerations we interpret the phase diagrams in terms of their stability. Simulations of various wetting and drying scenarios allow us to rationalize the dynamic behavior of the system and its relation to the equilibrium properties of wetting and drying.The Journal of Chemical Physics 03/2012; 136(12):124113. · 3.12 Impact Factor - [Show abstract] [Hide abstract]

**ABSTRACT:**Density functional approach is applied to study the phase behavior of Lennard-Jones(12,6) fluid in pillared slit-like pores. Our focus is in the evaluation of phase transitions in fluid adsorbed in the pore of a fixed width. If the length of pillars is sufficiently large, we observe additional phase transitions of the first and second order due to the symmetry breaking of the distribution of chain segments and fluid species with respect to the slit-like pore center. Re-entrant symmetry changes and additional critical, critical end points and tricritical points then are observed. The scenario of phase changes is sensitive to the energy of fluid-solid interaction, the amount, and the length of the pillars. Quantitative trends and qualitative changes of the phase diagrams topology are examined depending on the values of these parameters.The Journal of Chemical Physics 08/2011; 135(5):054703. · 3.12 Impact Factor -
##### Article: Full correspondence between asymmetric filling of slits and first-order phase transition lines

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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.AIP Advances. 11/2011; 1(4).

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