Free energy landscape within the hysteresis regime for fluids confined in disordered mesoporous solids

Adsorption/desorption and melting/freezing in structurally disordered nanoporous solids exhibit strongly non-equilibrium behavior as revealed by the formation of a hysteresis region populated by the multitude of different states. Many questions concerning the free energy spectrum of these states, including the existence of the equilibrium transition, if any, their accessibility in the experiments, and internal relaxation dynamics toward the global energy minimum, still remain poorly addressed. By using a serially connected pore model with the statistical disorder as a minimal model of the pore networks, we explore the system free energies along the solid-liquid and liquid-gas transitions in the pore systems. The rigorous results obtained with this model shed light on the occurrence and nature of the equilibrium transition line in porous solids with arbitrary pore topology. We discuss further the free energies along the experimentally measured boundary and scanning transitions and how close the equilibrium states can be approached in these experiments. (C) 2022 Author(s).

Automated summary

Adsorption/desorption and melting/freezing in structurally disordered nanoporous solids exhibit strongly non-equilibrium behavior. However, many questions related to the free energy spectrum, existence and accessibility of equilibrium transitions, and relaxation dynamics towards the global energy minimum, still remain poorly addressed. In this study, a minimal model of pore networks with statistical disorder is used to explore the system free energies along solid-liquid and liquid-gas transitions. The rigorous results obtained provide insights into the equilibrium transition line in porous solids with arbitrary pore topology.