A computer simulation study of tilted smetic mesophases.

Results are presented from a series of simulations undertaken to determine the effect of a novel form of molecular biaxiality upon the phase behaviour of the well established Gay-Berne (GB) liquid crystal model. Firstly, the simulation of a bulk system interacting via the Internally-Rotated Gay-Berne (IRGB) potential, which offers a single-site representation of a molecule rigidly constrained into a zig-zag conformation, is presented. The results of simulations performed for systems of IRGB particles with an aspect ratio of 3:1 confirm that the introduction of biaxiality into the model results in the destabilisation of the orientationally ordered phases. For particles with a sufficiently pronounced zig-zag conformation, this results in the complete destabilisation of the smectic A phase and the smectic B phase being replaced by the tilted smectic J phase. Following these observations, the effect upon the phase behaviour of increasing molecular elongation is also considered, with an increase in the aspect ratio from 3:1 to 4:1 resulting in the nematic and smectic J phases being replaced by smectic A and smectic G phases respectively. Secondly, a version of the IRGB potential modified to include a degree of molecular flexibility is considered. Results obtained from bulk systems interacting via the flexible IRGB for 3:1 and 4:1 molecules show that the introduction of flexibility results in the destabilisation of the smectic A phase and the stabilisation of the nematic and tilted hexatic phases. Finally, the effect upon the phase behaviour of the rigid IRGB model of the inclusion of a longitudinal linear quadrupole is examined. These results show that increasing quadrupole moment results in the destabilisation of the tilted hexatic phase, although the biaxial order parameter is increased with increasing quadrupole moment. There is no clear correlation between quadrupole magnitude and the other observed phase transitions, with the nematic and smectic A phases being variously stabilised and destabilised with increasing quadrupole magnitude. For the 4:1 molecules with large quadrupole moments, buckled smectic layers are observed where some molecules are tilted with respect to a local layer normal. Of all the systems considered here, this buckled structure is the one which most closely resembles the elusive smectic C phase.