A dynamical theory of homogeneous nucleation for colloids and macromolecules

Abstract

Homogeneous nucleation is formulated within the context of fluctuating hydrodynamics. It is shown that for a colloidal or macromolecular system in the strong damping limit the most likely path for nucleation can be determined by gradient descent in density space governed by a nontrivial metric fixed by the dynamics. The theory provides a justification and extension of more heuristic equilibrium approaches based solely on the free energy. It is illustrated by application to liquid-vapor nucleation where it is shown that, in contrast to most free energy-based studies, the smallest clusters correspond to long wavelength, small amplitude perturbations.