The classical theory of multicomponent nucleation, including binary nucleation, ternary nucleation, etc., makes similar key assumptions as in CNT for single-component nucleation. Clusters are modeled as spherical liquid droplets consisting of an ideal multicomponent solution. The surface tension is assumed to equal that of a flat surface of liquid having the same composition, in equilibrium with its multicomponent vapor. The Gibbs free energy of cluster formation is a function of the cluster’s size and composition and of the gas-phase partial pressures of each component. The critical size and composition are found at a saddle point on the multidimensional free energy surface, where the free energy of cluster formation is a maximum in one direction and a minimum in all orthogonal directions. Several improvements have been proposed within the framework of classical theory. These include models of the cluster growth trajectory near the critical point; studies that account for composition-dependent surface tension; and models that consider the existence of surface-active layers that cause the chemical composition near the cluster surface to be different than in the core.

Gas-phase nucleation of condensed-phase particles is important in many contexts, including interstellar dust formation, air pollution, global climate change, combustion and fires, semiconductor processing, and synthesis of nanoparticles for practical applications. Nucleation occurs via the growth of atomic or molecular clusters to “critical size” – the size where further growth is irreversible. These critical-size clusters are the nuclei for particle formation, and the growth of clusters to the size of nuclei is the concern of nucleation theory. Various scenarios occur, including single-component homogeneous nucleation from a supersaturated vapor, multicomponent nucleation, ion-induced nucleation, chemical nucleation, and nucleation in plasmas. Classical nucleation theory, which treats small clusters as having the same properties as the bulk condensed phase, is still widely used to estimate nucleation rates for many kinds of systems. However, it is anticipated that atomistic approaches based on computational chemistry will increasingly be used to facilitate more accurate predictions of gas-phase nucleation rates for substances and chemical systems of interest.