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Updated: Jul 16, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Theory of anomalous critical-cluster content in high-pressure binary nucleation
1Twister Supersonic Gas Solutions, Einsteinlaan 10, 2289 CC Rijswijk, The Netherlands. Vitaly.Kalikmanov@twisterbv.com
Abstract:
Nucleation experiments in binary (a-b) mixtures, when component a is supersaturated and b (carrier gas) is undersaturated, reveal that for some mixtures at high pressures the a content of the critical cluster dramatically decreases with pressure contrary to expectations based on classical nucleation theory. We show that this phenomenon is a manifestation of the dominant role of the unlike interactions at high pressures resulting in the negative partial molar volume of component a in the vapor phase beyond the compensation pressure. The analysis is based on the pressure nucleation theorem for multicomponent systems which is invariant to a nucleation model.
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