Frank Elastic Constants of Associating Rigid-Rodlike Systems

Abstract

Frank elastic constants of associating rigid rodlike systems are investigated using a mean field theory combined with the Straley elastic free energy formalism. The aggregation equilibrium and orientational ordering are treated self-consistently to analyze the concentration and temperature dependences of the elastic constants. Both a monomer--dimer model and a fully polydisperse rodlike aggregate model are considered. We find that aggregation selectively enhances the bend elastic constant through the long-tail structure of the aggregate-size distribution. As a result, a pronounced elastic anisotropy, $K_{33}\gg K_{11}>K_{22}$, emerges in the nematic phase. Decreasing temperature or increasing concentration promotes the formation of long rodlike aggregates and induces a rapid increase in the bend elastic constant, while the relation $K_{11}=3K_{22}$ remains unchanged. The exceptionally large bend elastic constants predicted here should be regarded as upper-bound estimates for the rigid-aggregate limit.