Capillary effects in a confined smectic phase of hard spherocylinders: influence of particle elongation

A system of hard rods confined into a pore with slit geometry (two parallel planar substrates) is studied theoretically in the regime of high packing fraction. In this regime the bulk system exhibits a nematic phase as well as a smectic-A (spatially layered) phase. When the system is confined, strong commensuration effects between the layer spacing and the pore width bring about a rich phenomenology, with a phase diagram showing layering and capillary transitions. The latter include capillary smectization transitions whereby a confined smectic phase occurs at conditions of saturation different from those of the corresponding bulk fluid. These transitions are seen to be intimately connected with layering transitions involving discontinuous changes in the number of layers inside the pore. This rich phenomenology is obtained by use of a sophisticated density-functional, Onsager-theory-based approach, especially suited to deal with strongly inhomogeneous fluids. The theory allows for a unified description of ordering and phase behavior of the fluid in confined geometry, and permits us to correlate the above behavior with the wetting properties of the fluid on a single substrate.