Mean-field density functional theory of a nanoconfined classical, three-dimensional Heisenberg fluid. I. The role of molecular anchoring.

In this work, we employ classical density functional theory (DFT) to investigate for the first time equilibrium properties of a Heisenberg fluid confined to nanoscopic slit pores of variable width. Within DFT pair correlations are treated at modified mean-field level. We consider three types of walls: hard ones, where the fluid-wall potential becomes infinite upon molecular contact but vanishes otherwise, and hard walls with superimposed short-range attraction with and without explicit orientation dependence. To model the distance dependence of the attractions, we employ a Yukawa potential. The orientation dependence is realized through anchoring of molecules at the substrates, i.e., an energetic discrimination of specific molecular orientations. If the walls are hard or attractive without specific anchoring, the results are "quasi-bulk"-like in that they can be linked to a confinement-induced reduction of the bulk mean field. In these cases, the precise nature of the walls is completely irrelevant at coexistence. Only for specific anchoring nontrivial features arise, because then the fluid-wall interaction potential affects the orientation distribution function in a nontrivial way and thus appears explicitly in the Euler-Lagrange equations to be solved for minima of the grand potential of coexisting phases.

Condensation, demixing, and orientational ordering of magnetic colloidal suspensions.

In this work we study the phase behavior of magnetic particles suspended in a simple nonmagnetic solvent. Magnetic particles are modelled as spherical particles carrying a three-dimensional, classical Heisenberg spin, whereas solvent molecules are treated as spherically symmetric Lennard-Jones particles. The binary mixture of magnetic particles and solvent is studied within the framework of classical density functional theory (DFT). Within DFT pair correlations are treated at the modified mean-field level at which they are approximated by orientation dependent Mayer f functions. In the absence of an external magnetic field four generic types of phase diagrams are observed depending on the concentration of magnetic particles. In this case we observe liquid-liquid phase coexistence between an orientationally ordered (polarized) and a disordered phase characterized by slightly different concentrations of magnetic particles. Liquid-liquid phase coexistence is suppressed by an external field and vanishes completely if the strength of the field is sufficiently large.