Structure and thermodynamics of anisotropic polymer fluids

Abstract

We investigate the structure and thermodynamics of anisotropic polymer fluids, focusing on the nematic phases of flexible polymers. The chains interact only through monomer–monomer excluded-volume interactions. As a function of an externally provided alignment along a fixed nematic director, we calculate the anisotropic pair correlation function, and demonstrate the existence of two density correlation lengths, ξ⊥ and ξz, controlling transverse and longitudinal density fluctuations, respectively. We allow the possibility that the chains align either along the director (nematic conformations), or are anti-aligned in a “discotic-like” configuration. The cohesive contribution to the free energy is established in a high-temperature approximation, and its sensitivity to the orientation of the chains is probed. Our approach is not limited to homogeneous liquid crystalline phases, but applies in any circumstance when the orientation of otherwise disordered polymers is the physically controlling effect, e.g., confinement in thin films or pores, shear-alignment of flexible polymers, or straining a cross-linked rubber network.