Dielectric and phase behavior of dipolar spheroids

The Stockmayer fluid, composed of dipolar spheres, has a well-known isotropic-ferroelectric phase transition at high dipole densities. However, there has been little investigation of the ferroelectric transition in nearly spherical fluids at dipole densities corresponding to those found in many polar solvents and in guest-host organic electro-optic materials. In this work, we examine the transition to ordered phases of low-aspect-ratio spheroids under both unperturbed and poled conditions, characterizing both the static dielectric response and thermodynamic properties of spheroidal systems. Spontaneous ferroelectric ordering was confined to a small region of aspect ratios about unity, indicating that subtle changes in sterics can have substantial influence on the behavior of coarse-grained liquid models. Our results demonstrate the importance of molecular shape in obtaining even qualitatively correct dielectric responses and provide an explanation for the success of the Onsager model as a phenomenological representation for the dielectric behavior of polar organic liquids.