Nucleation in cylindrical capillaries

We use a local density functional theory in the square gradient approximation to explore the properties of critical nuclei for the liquid-vapor transition of van der Waals fluids in cylindrical capillaries. The proposed model allows us to investigate the effect of pore size, surface field, and supersaturation on the behavior of the system. Our calculations predict the existence of at least three different pathways for the nucleation of droplets and bubbles in these confined fluids: axisymmetric annular bumps and lenses, and asymmetric droplets. The morphological transition between these different structures is driven by the existence of states of zero compressibility in the capillary. We show that the classical capillarity theory provides surprisingly accurate predictions for the work of formation of critical nuclei in cylindrical pores when line tension contributions to the free energy are taken into account.