The Effects of Spatial Correlations on Steady State Nucleation Kinetics in Dense Fluid Systems
Journal of Statistical Physics
A widely used expression for the steady-state nucleation rate is determined, in part, by the concentration of critical nuclei in a constrained equilibrium state of the system under consideration. We show that when a dense solvent is present, the values of the constrained equilibrium concentrations reflect the spatial correlations that arise from reactant-solvent molecule collisions. We evaluate the effect of such correlations for a simple, model fluid in terms of measurable reaction rate constants; our analysis shows that correlations influence each step in the multistep process of cluster formation and that the overall impact on the nucleation rate is cumulative. We argue that the very low, homogeneous nucleation rates observed in certain miscibility gap experiments are easily understood in the context of our analysis.
D. Peak and J.W. Corbett, "The Effects of Spatial Correlations on Steady State Nucleation Kinetics in Dense Fluid Systems," Journal of Statistical Physics 17, 97-110 (1977).