CLUSTER APPROACH TO THE KINETIC-THEORY OF HOMOGENEOUS NUCLEATION

A new, self-consistent formulation of the homogeneous nucleation theory has been proposed. This approach differs from the classical Becker-Doring-Zel'dovich theory in two respects: i) evaporation rates are evaluated by referring to the stable equilibrium of a saturated vapour rather than to the constrained metastable equilibrium of a supersaturated vapour; ii) for the reference stable equilibrium state the Fisher theory of condensation is used in order to obtain a self-consistent definition of the energy barrier for 1-cluster formation. The present theory has no adjustable parameters. A comparison of the new expressions for the nucleation rate and critical cluster size with the corresponding classical expressions has been made for the different parts of the phase diagram (temperature-supersaturation) and the domain where both theories are close has been found. It has been shown that the present theory has much better agreement with experimental results for n-nonane than the classical one.