Density-functional theory of the kinetics of crystallization of hard-sphere suspensions: Single conserved order parameter

Publisher Website
Google Scholar
Abstract
A theoretical study is presented of the kinetics of crystallization of a hard-sphere-like colloidal suspension in a fixed volume based upon the use of time-dependent density-functional theory incorporating conserved particle dynamics. Distinguishing crystalline order by the particle density alone, we demonstrate that the constraints of fixed number and volume lead naturally to the appearance of a new nonuniform minimum in the free energy corresponding the equilibrium coexistence between crystalline order and disordered suspension. Using numerical integration, we follow the time dependence of a range of initial spherical crystallites. The normal and tangential osmotic pressure fields about these growing crystallites are presented and the growing crystallite is shown to be isolated from the higher pressure of the surrounding disordered suspension by the nonequilibrium depletion zone which surrounds it. These results are compared with recent light-scattering studies.