DENSITY-FUNCTIONAL THEORY OF THE KINETICS OF CRYSTALLIZATION OF HARD-SPHERE SUSPENSIONS - SINGLE CONSERVED ORDER-PARAMETER

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 cons erved par tide dynamics. Distinguishing crystalline order by the parti cle density alone, we demonstrate that the constraints of fixed number and volume lead naturally to the appearance of a new nonuniform minim um in the free energy corresponding the equilibrium coexistence betwee n crystalline order and disordered suspension. Using numerical integra tion, we follow the time dependence of a ran of initial spherical crys tallites. The normal and tangential osmotic pressure fields about thes e growing crystallites are presented and the growing crystallite is sh own to be isolated from the higher pressure of the surrounding disorde red suspension by the nonequilibrium depletion zone which surrounds it . These results are compared with recent light-scattering studies.