Exhaustion of Nucleation in a Closed System

Abstract

We determine the distribution of cluster sizes that emerges from an initial phase of homogeneous aggregation with conserved total particle density. The physical ingredients behind the predictions are essentially classical: Super-critical nuclei are created at the Zeldovich rate, and before the depletion of monomers is significant, the characteristic cluster size is so large that the clusters undergo diffusion limited growth. Mathematically, the distribution of cluster sizes satisfies an advection PDE in "size-space". During this creation phase, clusters are nucleated and then grow to a size much larger than the critical size, so nucleation of super-critical clusters at the Zeldovich rate is represented by an effective boundary condition at zero size. The advection PDE subject to the effective boundary condition constitutes a "creation signaling problem" for the evolving distribution of cluster sizes during the creation era. Dominant balance arguments applied to the advection signaling problem show that the characteristic time and cluster size of the creation era are exponentially large in the initial free-energy barrier against nucleation, G_*. Specifically, the characteristic time is proportional to exp(2 G_*/ 5 k_B T) and the characteristic number of monomers in a cluster is proportional to exp(3G_*/5 k_B T). The exponentially large characteristic time and cluster size give a-posteriori validation of the mathematical signaling problem. In a short note, Marchenko obtained these exponentials and the numerical pre-factors, 2/5 and 3/5. Our work adds the actual solution of the kinetic model implied by these scalings, and the basis for connection to subsequent stages of the aggregation process after the creation era.