Polydispersity and ordered phases in solutions of rodlike macromolecules.

1 Max-Planck-Institut für Polymerforschung, D-55021 Mainz, Postfach 3148, FRG Institute of Physical Chemistry PAS and College of Sciences Dept. III, Kasprzaka 44/52, 01224 Warsaw, Poland Abstract We apply density functional theory to study the influence of polydispersity on the stability of columnar, smectic and solid ordering in the solutions of rodlike macromolecules. For sufficiently large length polydispersity (standard deviation σ > 0.25) a direct first-order nematic-columnar transition is found, while for smaller σ there is a continuous nematic-smectic and first-order smectic-columnar transition. For increasing polydispersity the columnar structure is stabilized with respect to solid perturbations. The length distribution of macromolecules changes neither at the nematic-smectic nor at the nematic-columnar transition, but it does change at the smectic-columnar phase transition. We also study the phase behaviour of binary mixtures, in which the nematic-smectic transition is again found to be continuous. Demixing according to rod length in the smectic phase is always preempted by transitions to solid or columnar ordering. PACS numbers: 87.15.Da, 64.70.M, 61.30.Cz.