Translational and rotational diffusion of rod shaped molecules by molecular dynamics simulations

Abstract

The results of molecular dynamics simulations of the dynamical evolution of assemblies of linear rigid rods of variable aspect ratio, a, and number density, ρ, in the isotropic phase are reported. The rods consist of m equally spaced sites interacting with the Weeks-Chandler-Andersen repulsive pair potential, where 2 < m < 16. With increasing m, features specific to long rods, such as anisotropic self-diffusion, become apparent. There is also an increasing separation between the characteristic relaxation times of the torque, angular velocity, and reorientational time correlation functions with increasing density. The latter is exponential at high densities even for dimers. The isotropic translational diffusion coefficient, Di, and rotational diffusion coefficient, Dr, are reported as a function of m and ρ or volume fraction, ξ. The mDi data scale with ξ throughout much of the simulated range, while the rotational diffusion coefficients scale approximately as m3Dr against ρ at low densities but as ∼m6Dr at high ρ, consistent with theories of colloidal and noncolloidal rod-containing liquids. The crossover density between the two regimes is parameterized in analytic form. The probability distribution functions for displacements and angular jumps in a given time show evidence of non-Gaussian behavior with increasing density. The shear viscosity and Di scale approximately as m and m-1, respectively, in the semidilute regime, which is consistent with a Stokes-Einstein-like relationship. At high concentrations, a frustrated or glassy structure formed in which the rods were randomly oriented.