Dipolar interactions, molecular flexibility, and flexoelectricity in bent-core liquid crystals

J Chem Phys. 2005 Nov 1;123(17):174907. doi: 10.1063/1.2062007.


The effects of dipolar interactions and molecular flexibility on the structure and phase behavior of bent-core molecular fluids are studied using Monte Carlo computer simulations. Some calculations of flexoelectric coefficients are also reported. The rigid cores of the model molecules consist of either five or seven soft spheres arranged in a "V" shape with external bend angle gamma. With purely repulsive sphere-sphere interactions and gamma = 0 degrees (linear molecules) the seven-sphere model exhibits isotropic, uniaxial nematic, and untilted and tilted smectic phases. With gamma > or = 20 degrees the untilted smectic phases disappear, while the system with gamma > or = 40 degrees shows a direct tilted smectic-isotropic fluid transition. The addition of electrostatic interactions between transverse dipole moments on the apical spheres is generally seen to reduce the degree of molecular inclination in tilted phases, and destabilizes the nematic and untilted smectic phases of linear molecules. The effects of adding three-segment flexible tails to the ends of five-sphere bent-core molecules are examined using configurational-bias Monte Carlo simulations. Only isotropic and smectic phases are observed. On the one hand, molecular flexibility gives rise to pronounced fluctuations in the smectic-layer structure, bringing the simulated system in better correspondence with real materials; on the other hand, the smectic phase shows almost no tilt. Lastly, the flexoelectric coefficients of various nematic phases--with and without attractive sphere-sphere interactions--are presented. The results are encouraging, but a large computational effort is required to evaluate the appropriate fluctuation relations reliably.