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Title: Influence of system size on the properties of a fluid adsorbed in a nanopore: Physical manifestations and methodological consequences

Hysteresis and discontinuities in the isotherms of a fluid adsorbed in a nanopore in general hamper the determination of equilibrium thermodynamic properties, even in computer simulations. A way around this has been to consider both a reservoir of small size and a pore of small extent in order to restrict the fluctuations of density and approach a classical van der Waals loop. We assess this suggestion by thoroughly studying through Monte Carlo simulations and density functional theory the influence of system size on the equilibrium configurations of the adsorbed fluid and on the resulting isotherms. We stress the importance of pore-symmetry-breaking states that even for modest pore sizes lead to discontinuous isotherms and we discuss the physical relevance of these states and the methodological consequences for computing thermodynamic quantities.
Authors:
 [1] ; ;  [2]
  1. CRMD, CNRS FRE 3520, Université d'Orléans, 1b rue de la Férollerie, 45071 Orléans Cedex 02 (France)
  2. LPTMC, CNRS UMR 7600, Université Pierre et Marie Curie, boîte 121, 4 place Jussieu, 75252 Paris Cedex 05 (France)
Publication Date:
OSTI Identifier:
22419962
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPUTERIZED SIMULATION; DENSITY FUNCTIONAL METHOD; ISOTHERMS; MONTE CARLO METHOD; THERMODYNAMIC PROPERTIES; VAN DER WAALS FORCES