Role of dipole elongation in orientationally ordered liquids

Abstract

A recent study shows that the dipole elongation in the extended dipole model plays a significant role in the phase transitions of liquid crystal phases. In this paper, molecular dynamics (MD) simulations were performed for the dipole model with different distances between the two charges keeping the total dipole moment the same. The potential energy consists of the Lennard-Jones potential and the site-site electrostatic contribution of partial charges. Detailed analyses were made with respect to the average order parameters (P(1)) and (P(2)) as functions of density along with other thermodynamic properties. When the reduced dipole elongations are 0.16 and 0.32, respectively, it is shown that the chainlike structures in the low density regime, liquid phases with columnar and smectic orders, and solid phases are formed; the phase with nematic order is not present anymore. At 0.64, the phases with antiferroelectric order were favored. The transition is found at the reduced elongation 0.55. It shows that the phase transitions are quite sensitive to the molecular charge distribution; this simple system could exhibit rather rich phase behaviors, which represents a significant advance in identifying molecular and state parameters of the future ferroelectric liquids.