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-DSring-Zel'dovich theory in tworespects: I) evaporation rates are evaluated by referring to the stable equilibrium of a saturatedvapour rather than to the constrained metastable equilibrium of a supersaturated vapour; ii) forthe reference stable equilibrium state the Fisher theory of condensation is used in order to obtaina self-consistent definition of the energy barrier for ¿-cluster formation. The present theory hasno adjustable parameters. A comparison of the new expressions for the nucleation rate andcritical cluster size with the corresponding classical expressions has been made for the differentparts of the phase diagram (temperature-supersaturation) and the domain where both theoriesare close has been found. It has been shown that the present theory has much better agreementwith experimental results for w-nonane than the classical one.