Simulation insights into the role of antiparallel molecular association in the formation of smectic A phases

Abstract

A simple dissipative particle dynamics (DPD) model is introduced, which can be used to represent a broad range of calamitic mesogens. The model allows for antiparallel association that occurs naturally in a number of mesogens with terminal dipoles, including the 4-n-alkyl-4′-cyanobiphenyl (nCB) series. Favourable antiparallel interactions lead to the formation of SmA_d phases in which the layer spacing is intermediate between monolayer and bilayer. The model is easily tuned to vary the strength of antiparallel association and the SmA layer spacing, and to give either isotropic–smectic or isotropic–nematic–smectic phase sequences. The model allows for a range of other smectics: including SmA₁ phases exhibiting microphase separation within layers, and smectics A structures with more complicated repeat units. For large system sizes (≥50 000 molecules) in the nematic phase, we are able to demonstrate the formation of three distinct types of cybotactic domains depending on the local interactions. Cybotactic domains are found to grow in the nematic–smectic pretransitional region as the system moves closer to T_SN.