Role of length polydispersity in the phase behavior of freely rotating hard-rectangle fluids.

Abstract

We use the density-functional formalism, in particular the scaled-particle theory, applied to a length-polydisperse hard-rectangle fluid to study its phase behavior as a function of the mean particle aspect ratio κ_{0} and polydispersity Δ_{0}. The numerical solutions of the coexistence equations are calculated by transforming the original problem with infinite degrees of freedoms to a finite set of equations for the amplitudes of the Fourier expansion of the moments of the density profiles. We divide the study into two parts. The first one is devoted to the calculation of the phase diagrams in the packing fraction η_{0}-κ_{0} plane for a fixed Δ_{0} and selecting parent distribution functions with exponential (the Schulz distribution) or Gaussian decays. In the second part we study the phase behavior in the η_{0}-Δ_{0} plane for fixed κ_{0} while Δ_{0} is changed. We characterize in detail the orientational ordering of particles and the fractionation of different species between the coexisting phases. Also we study the character (second vs first order) of the isotropic-nematic phase transition as a function of polydispersity. We particularly focus on the stability of the tetratic phase as a function of κ_{0} and Δ_{0}. The isotropic-nematic transition becomes strongly of first order when polydispersity is increased: The coexistence gap widens and the location of the tricritical point moves to higher values of κ_{0} while the tetratic phase is slightly destabilized with respect to the nematic one. The results obtained here can be tested in experiments on shaken monolayers of granular rods.