Physical clusters in nucleation theory

Abstract

We examine the general problem of calculating from microscopic principles the equilibrium distribution of physical clusters demanded by the theory of homogeneous nucleation. We direct attention specially to the effect of interference between clusters. In a one‐dimensional fluid where interference is accounted for by the ’’most probable length’’ approximation developed earlier, we show that the effect is negligible under conditions corresponding to nucleation experiments. Also in one dimension, we show that cluster partition functions appearing in the theory are numerically very well approximated by calculations based on the definition of Lee, Barker, and Abraham (LBA). We therefore argue that in three dimensions the distribution of clusters for nucleation theory can be obtained from the familiar mass‐action law, in which cluster partition functions are calculated by the method of LBA.