Extending classical nucleation theory to confined systems

TL;DR

This paper extends classical nucleation theory to confined systems, analyzing how finite size and interfacial width affect nucleation rates and barriers in small pores and vesicles.

Contribution

It introduces a modified nucleation theory accounting for system size limitations and interfacial width effects, advancing understanding of nucleation in confined environments.

Findings

Finite system size limits supercritical cluster growth.

Nucleation rate decreases with decreasing system size.

Relaxing the zero interfacial width assumption significantly alters nucleation barriers.

Abstract

Classical nucleation theory has been recently reformulated based on fluctuating hydrodynamics [J.F. Lutsko and M.A. Dur\'{a}n-Olivencia, J. Chem. Phys. 138, 244908 (2013)]. The present work extends this effort to the case of nucleation in confined systems such as small pores and vesicles. The finite available mass imposes a maximal supercritical cluster size and prohibits nucleation altogether if the system is too small. We quantity the effect of system size on the nuceation rate. We also discuss the effect of relaxing the capillary-model assumption of zero interfacial width resulting in significant changes in the nucleation barrier and nucleation rate.