Mesoscopic theory for systems with competing interactions near a confining wall.

Abstract

Mesoscopic theory for self-assembling systems near a planar confining surface is developed. Euler-Lagrange equations and the boundary conditions (BCs) for the local volume fraction and the correlation function are derived from the density functional theory expression for the grand thermodynamic potential. Various levels of approximation can be considered for the obtained equations. The lowest-order nontrivial approximation [generic model (GM)] resembles the Landau-Brazovskii-type theory for a semi-infinite system. Unlike in the original phenomenological theory, however, all coefficients in our equations and BCs are expressed in terms of the interaction potential and the thermodynamic state. Analytical solutions of the linearized equations in the GM are presented and discussed on a general level and for a particular example of the double-Yukawa potential. We show exponentially damped oscillations of the volume fraction and the correlation function in the direction perpendicular to the confining surface. The correlations show oscillatory decay in directions parallel to this surface too, with the decay length increasing significantly when the system boundary is approached. The framework of our theory allows for a systematic improvement of the accuracy of the results.