Capillary condensation and orientational ordering of confined polar fluids.

The phase behavior and the orientational structure of polar model fluids confined to slit pores is investigated by means of density functional theory in a modified mean-field approximation. We focus on fluid states and further assume a uniform number density throughout the pore. Our results for spherical dipolar particles with additional van der Waals-like interactions (Stockmayer fluids) reveal complex fluid-fluid phase behavior involving condensation and first- and second-order isotropic-to-ferroelectric phase transitions, where the ferroelectric ordering occurs parallel to the confining walls. The relative importance of these phase transitions depends on two "tuning" parameters, that is the strength of the dipolar interactions (relative to the isotropic attractive ones) between fluid particles, and on the pore width. In particular, in narrow pores the condensation transition seen in bulk Stockmayer fluids is entirely suppressed. For dipolar hard spheres, on the other hand, the impact of confinement consists in a decrease of the isotropic-to-ferroelectric transition temperatures. We also demonstrate that the local orientational structure is inhomogeneous and anisotropic even in globally isotropic systems, in agreement with computer simulation results.