Short-time transport properties in dense suspensions: from neutral to charge-stabilized colloidal spheres

J Chem Phys. 2008 Mar 14;128(10):104903. doi: 10.1063/1.2868773.


We present a detailed study of short-time dynamic properties in concentrated suspensions of charge-stabilized and of neutral colloidal spheres. The particles in many of these systems are subject to significant many-body hydrodynamic interactions. A recently developed accelerated Stokesian dynamics (ASD) simulation method is used to calculate hydrodynamic functions, wave-number-dependent collective diffusion coefficients, self-diffusion and sedimentation coefficients, and high-frequency limiting viscosities. The dynamic properties are discussed in dependence on the particle concentration and salt content. Our ASD simulation results are compared with existing theoretical predictions, notably those of the renormalized density fluctuation expansion method of Beenakker and Mazur [Physica A 126, 349 (1984)], and earlier simulation data on hard spheres. The range of applicability and the accuracy of various theoretical expressions for short-time properties are explored through comparison with the simulation data. We analyze, in particular, the validity of generalized Stokes-Einstein relations relating short-time diffusion properties to the high-frequency limiting viscosity, and we point to the distinctly different behavior of de-ionized charge-stabilized systems in comparison to hard spheres.