Connecting dynamic pore filling mechanisms with equilibrium and out of equilibrium configurations of fluids in nanopores

Abstract

In the present study, using dynamic mean field theory complemented by grand canonical molecular dynamics simulations, we investigate the extent to which the density distributions encountered during the dynamics of capillary condensation are related to those distributions at equilibrium or metastable equilibrium in a system at fixed average density (canonical ensemble). We find that the states encountered can be categorized as out of equilibrium or quasi-equilibrium based on the magnitude of the driving force for mass transfer. More specifically, in open-ended slit pores, pore filling via double bridging is an out of equilibrium process, induced by the dynamics of the system, while pore filling by single bridge formation is connected to a series of configurations that are equilibrium configurations in the canonical ensemble and that cannot be observed experimentally by a standard adsorption process, corresponding to the grand canonical ensemble. Likewise, in closed cap slits, the formation of a liquid bridge near the pore opening and its subsequent growth while the initially detached meniscus from the capped end remains immobilized are out of equilibrium processes that occur at large driving forces. On the other hand, at small driving forces, there is a continuous acceleration of the detached meniscus from the capped end, which is associated with complete reversibility in the limit of an infinitesimally small driving force.