Monte Carlo Studies of the Structural and Thermodynamic Properties of Some Smectic and Ferroelectric Liquid Crystals

Monte Carlo simulation based on the Gaussian overlap model was used to study the thermodynamic properties of smectic C: C₅H₁₁O–(OH)C₆H₃–CH=N–C₆H₄–C₅H₁₁ (A), C₁₀H₂₁O–C₆H₄–CH=CH–C₆H₄–OC₁₀H₂₁ (B), ferroelectric smectic C* liquid crystals (LC): C₇H₁₅O–C₆H₄–C₆H₄–COO–CH₂C*H(CH₃)C₂H₅ (C), C₈H₁₇O–C₆H₄–C₆H₄–C₂H₄C*H(CH₃)C₂H₅ (D), and an equimolar mixture of {A+C} and {A+D}. A system of N = 125 pairwise interacting ellipsoids of revolution placed in a volume V at a temperature T (that is, a system described by a canonical NVT-ensemble) is considered. These interactions were calculated using a specially devised Lennard-Jones potential, allowing for both mild anisotropic repulsion of particles (ellipsoids) and their dispersion attraction. Dipole–dipole interactions were also taken into account, since the molecules have highly polar groups: –O–, OH, CH=N, and COO and hence a high dipole moment (4.2-5.3 D). Calculations were carried out for a rectangular parallelepiped with periodic boundary conditions imposed on its faces. An elementary object of the NVT-ensemble was a two-molecule microcluster (dimer) but not a single molecule from the group under study. Smectic A ordering in the system has been unambiguously proven for different temperatures and fixed densities (0.32 0.44, where is the close packing coefficient). The ordering is attributed to the large (transverse) dipole moment inherent in molecules {A}-{D}. Temperature dependences of free energy, configuration energy, heat capacity C_v, and orientational order parameter were obtained. The curves agree well with the experimental data on variation of the properties of smectic LC.