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. ͓S1063-651X͑97͒06409-X͔

A theoretical study is presented on the kinetics of crystallization of a colloidal suspension in a fixed volume based upon the use of time dependent density functional theory incorporating conserved particle and nonconserved structure dynamics. This is a continuation of previous work done with conserved particle dynamics alone. The constraints of fixed number and volume lead to nonuniform solutions to the time independent equations of motion. One of the nonuniform solutions is found to have the minimum free energy and is identified as the stable equilibrium coexistence of crystalline and disordered suspension. Numerical integration is used to follow the time dependent motion of a range of initial crystallites. A broadband of stationary states, additional to those identified analytically, are located by the numerical integration. We show that these solutions arise from pinning induced by the discretization of space. The normal and tangential osmotic pressure fields are given and the growing crystallite is shown to be isolated from the higher pressure of the surrounding disordered suspension by the nonequilibrium depletion zone that surrounds it. These results are compared with recent light scattering studies.

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