A comparison of dynamic mean field theory and grand canonical molecular dynamics for the dynamics of pore filling and capillary condensation of fluids in mesopores
A Rathi and ES Kikkinides and DM Ford and PA Monson, JOURNAL OF CHEMICAL PHYSICS, 149, 014703 (2018).
We use results from grand canonical molecular dynamics (GCMD) to test the predictions from dynamic mean field theory (DMFT) for the pore filling and capillary condensation mechanisms of a fluid confined in slit shaped mesopores. The theory predicts that capillary condensation occurs by a nucleation process in which a liquid bridge forms between the two walls, and the pore is filled via the growth of this bridge. For longer pores, multiple bridging is seen. These mechanisms are confirmed by the molecular dynamics simulations. The primary difference between the theory and simulations lies in the role of fluctuations. DMFT predicts a single nucleation time and location, while in GCMD (and in nature) a distribution of nucleation times and locations is seen. Published by AIP Publishing.
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