Structure and dielectric properties of polar fluids with extended dipoles: results from numerical simulations

Abstract

The strengths and shortcomings of the point dipole model for polar fluids of spherical molecules are illustrated by considering the physically more relevant case of extended dipoles formed by two opposite charges ± q separated by a distance d (dipole moment μ=qd). Extensive molecular dynamics simulations on a high-density dipolar fluid are used to analyse the dependence of the pair structure, dielectric constant ε and dynamics as a function of the ratio d/σ (σ is the molecular diameter), for a fixed dipole moment μ. The point dipole model is found to agree well with the extended dipole model up to d/σ ≃ 0.3. Beyond that ratio, ε shows a non-trivial variation with d/σ. When d/σ > 0.6, a transition is observed towards a hexagonal columnar phase; the corresponding value of the dipole moment is found to be substantially lower than the value of the point dipole required to drive a similar transition.