Generalized Onsager theory of liquid crystals

The Onsager theory is known to be inaccurate in its prediction of the critical transition density for small aspect ratio hard rods. In this paper we generalize the Onsager theory in two dimensions by taking into account the short-range order as well as the higher-order virial coefficients, up to the fourth order. By carrying out molecular dynamics (MD) simulations on "molecules" comprising linked hard disks with an aspect ratio ℓ ranging from 5 to 13, we show that the generalized theory is much improved as compared to the traditional theory, with its predictions of the transition density agreeing well with the simulation results. This indicates the importance of short-range order considerations (in conjunction with steric repulsion) for molecules with ℓ≤10, a group which includes the most commonly encountered thermotropic liquid crystals. MD simulations further yield evidence for hexagonal order for molecules with ℓ≤8, indicating an intermediate hexagonal phase before solidifying at higher densities.