Effect of flexibility of arms on the nematic ordering of V-shaped molecules

Abstract

The nematic ordering of a melt of V-shaped molecules composed of two semiflexible arms connected by one end at an external angle α is inspected within the Landau theory of phase transitions. The conformational statistics of arms is described by a discrete worm-like chain model. It is found that for a sufficiently high stiffness of the arms the phase diagram contains the regions of stability of isotropic (I), prolate (NU+) and oblate (NU−) uniaxial, and biaxial (NB) nematic phases. The isotropic–uniaxial nematic and uniaxial nematic – biaxial nematic phase transitions are of the first and second order, respectively. At lowering the stiffness of arms the stability area of NB phase decreases; the re-entrant NB phase becomes possible in the certain range of angles α and the sequence of phase transitions I−NU−−NB−NU+−NB occurs. At a sufficiently low stiffness, the stability region of the nematic biaxial phase disappears completely, and phase diagrams display only the first order transitions between I−NU+, I−NU−, and NU+−NU− phases. A further decrease in the stiffness of arms leaves only the first order I−NU+ transition in the phase diagrams. The tricritical points appear at the curves of NU−−NB transition in the phase diagrams in certain intervals of values of the stiffness parameter.