Smectic phase in a system of hard ellipsoids with isotropic attractive interactions.
The smectic phase is studied for a thermotropic fluid model consisting of aligned hard ellipsoids with superimposed square-well attractive interactions of variable range. The system is analyzed using a density functional theory in which the hard-core contributions to the free-energy functional are treated within a nonlocal weighted density approximation and the attractive contributions are considered at a mean-field level. In the absence of attractions the model reduces, under appropriate scaling, to a fluid of hard spheres and therefore does not exhibit smectic ordering. It is shown that above a certain value of the square-well range, smectic ordering is stable relative to the nematic state at densities well inside the fluid region. The nematic-smectic-A transition is found to be continuous at high temperatures and first order at low temperatures, these two regimes being separated by a tricritical point at an intermediate temperature. These predictions have been confirmed by computer simulation of the model fluid. The results highlight that smectic ordering can be stabilized by coupling anisotropic short-range repulsions with the isotropic contribution of the soft attractive interactions. By increasing the pressure, the range of stability of the smectic phase is seen to decrease. At sufficiently high pressure, the smectic phase is suppressed, and the solid phase dominates. Our calculations show that smectic ordering is no longer stable if the range of the attractions is made too long ranged.
del Río
Elvira Martín
EM
Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, United Kingdom.
de Miguel
Enrique
E