title: Many-Body Effects on the Thermodynamics of Fluids, Mixtures, and Nanoconfined Fluids.
abstract: Using expanded Wang-Landau simulations, we show that taking into account the many-body interactions results in sharp changes in the grand-canonical partition functions of single-component systems, binary mixtures, and nanoconfined fluids. The many-body contribution, modeled with a 3-body Axilrod-Teller-Muto term, results in shifts toward higher chemical potentials of the phase transitions from low-density phases to high-density phases and accounts for deviations of more than, e.g., 20% of the value of the partition function for a single-component liquid. Using the statistical mechanics formalism, we analyze how this contribution has a strong impact on some properties (e.g., pressure, coexisting densities, and enthalpy) and a moderate impact on others (e.g., Gibbs or Helmholtz free energies). We also characterize the effect of the 3-body terms on adsorption isotherms and adsorption thermodynamic properties, thereby providing a full picture of the effect of the 3-body contribution on the thermodynamics of nanoconfined fluids.
authors.affiliation: Department of Chemistry, University of North Dakota , Grand Forks, North Dakota 58202, United States.
authors.forename: Caroline
authors.initials: C
authors.lastname: Desgranges
authors.affiliation: Department of Chemistry, University of North Dakota , Grand Forks, North Dakota 58202, United States.
authors.forename: Jerome
authors.initials: J
authors.lastname: Delhommelle
mesh_terms: D001128:Argon / Q000737:chemistry*; D007726:Krypton / Q000737:chemistry*; D058608:Nanopores; D044367:Phase Transition; D013816:Thermodynamics; D014835:Volatilization
chemical_list: D007726:Krypton; D001128:Argon