Effective field of a dipole in non-polar polarizable fluids

Abstract

A theory of the effect of molecular polarizability on the equilibrium properties of dielectric liquids is developed, and then applied to study molecular dynamics calculations of the field of a dipole in non-polar polarizable fluids. The point of view is adopted that molecular polarizability arises because some intramolecular degrees of freedom give rise to single molecule dipole moment fluctuations. Thus intramolecular internal degrees of freedom are explicitly incorporated into a classical statistical mechanical description of the system. To compare with classical molecular dynamics results these internal degrees of freedom are modelled as Drude oscillators. The agreement with the computer simulation results is quite good. These results suggest that this method is capable of providing accurate and convenient descriptions of the effects of molecular polarizability in a variety of more complicated circumstances.