Free energy calculations along entropic pathways. III. Nucleation of capillary bridges and bubbles

摘要: Using molecular simulation, we analyze the capillary condensation and evaporation processes for argon confined in a cylindrical nanopore. For this purpose, define entropy of adsorbed fluid as reaction coordinate determine free energy associated with both along entropic pathways. condensation, identify complex profile resulting from multi-stage nature phenomenon. We find to proceed through nucleation liquid bridge across nanopore, followed by its expansion throughout pore give rise stable phase high density. In case evaporation, pathway also exhibits different regimes, corresponding initial destabilization layered structure formation, subsequent expansion, bubble