(514c) Molecular Driving Forces of Crystallization: A Study of the Crystal Growth Rate From the Fluctuation-Dissipation Theorem

A perennial challenge for crystal engineering is identification of thermodynamic conditions favoring crystal growth with controlled size and morphology. While experimental investigations are instrumental to understanding the effects of macroscopic variables on the kinetic processes, analysis and utilization of the experimental data toward a rational design require a fundamental knowledge linking molecular driving forces to thermodynamic variables dictating crystallization. In this work, the crystal growth rates are calculated from NVT molecular dynamics simulations based on the fluctuation-dissipation theorem. Special attention is given to the effect of intermolecular forces on the interfacial behavior and the kinetics of crystallization. By calculating of crystal growth rates at the (001) direction of model fluid-solid systems over a broad range of the parameter space, we find that crystal growth in protein solutions or in colloids can be qualitatively different from that in simple fluids and that the kinetics of colloidal crystallization can be achieved by an effective control of the potential of mean force in addition to thermodynamic conditions.