Relation between the grafting density of liquid crystal macromolecule and the symmetry of self-assembled bulk phase: Coarse-grainedmolecular dynamics study

Abstract

I consider a generic coarse-grained model suitable for the study of bulk self-assembly of liquid crystal (LC) macromolecules. The cases include LC dendrimers, gold nanoparticles modified by polymer chains with terminating LC groups and others. The study is focused on the relation between a number of grafted chains, Nch , and the symmetry of the self-assembled bulk phases. Simple space-filling arguments are used first to estimate stability intervals for a rod-like, disc-like and spherulitic conformations in terms of Nch . These are followed by coarse-grained molecular dynamics simulations for both spontaneous and aided self-assembly of LC macromolecules into bulk phases. In spontaneous self-assembly runs, essential coexistence of rod-like and disc-like conformations is observed (via analysis of the histograms for the molecular asphericity) in a broad interval of Nch , which prevents the formation of defect-free structures. The use of uniaxial and planar aiding fields is found to improve self-assembly intomonodomain phases by promoting conformations of respective symmetry. Strong shape-phase relation, observed experimentally, is also indicated by the simulations by the coincidence of the stability intervals for the respective conformations with those for the bulk phases. © J.M. Ilnytskyi, 2013.