Dynamics of a model colloidal suspension from dilute to freezing

S D W Hannam, P J Daivis, G Bryant

Molecular dynamics simulation was used to study a model colloidal suspension at a range of packing fractions from the dilute limit up to the freezing point. This study builds on previous work by the authors which modeled the colloidal particles with a hard core surrounded by a Weeks-Chandler-Anderson potential with modified interaction parameters, and included an explicit solvent. In this work, we study dynamical properties of the model by first calculating the velocity autocorrelation function, the self-diffusion coefficient, and the mutual diffusion coefficient. We also perform detailed calculations of the colloidal particle intermediate scattering function to study the change in dynamics leading up to the freezing point, and to determine whether the current model can be used to interpret light scattering experiments. We then perform a multiexponential analysis on the intermediate scattering function results and find that the data are fitted well by the sum of two exponentials, which is in line with previous analysis of experimental colloidal suspensions. The amplitudes and decay coefficients of the two modes are determined over a large range of wave vectors at packing fractions leading up to the freezing point. We found that the maximum wave vector at which macroscopic diffusive behavior was observed decreased as the packing fraction increased, and a simple extrapolation shows the maximum wave vector going to zero at the melting point. Lastly, the ratio of the two decay coefficients is compared to the scaling law proposed by Segrè and Pusey [Phys. Rev. Lett. 77, 771 (1996)PRLTAO0031-900710.1103/PhysRevLett.77.771]. It was found that the ratio was not constant, but instead was wave vector dependent.