Momentum and stress relaxation in fluids illustrating caging.
The self diffusion coefficient, shear viscosity, and velocity time correlation function are calculated for a hard sphere fluid under a severe assumption, namely, the friction arises from uncorrelated binary collisions and from correlated backscattering (caging) collisions as represented in the memory function. Relaxation of the memory function from its zerotime caging value is described as a diffusion process. Derived diffusion coefficients and the shear viscosities, relative to their Enskog values decrease and increase with density, respectively, in a monotonic and gradual fashion in contrast with simulation values that show a precipitous change near the fluid-solid transition. In the present pair diffusion model, the velocity time correlation function vanishes at the proper time but its tail is overly damped relative to the simulation data. A weak breakdown of the Stokes-Einstein relation is also predicted.
Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, USA.
Glenn T
GT
Evans