Integral equation theory for Lennard-Jones fluids: The bridge function and applications to pure fluids and mixtures

Abstract

The pure Lennard-Jones fluid and various binary mixtures of Lennard-Jones fluids are studied by both molecular dynamics simulation and with a new integral equation which is based on that proposed by Duh and Haymet recently [J. Chem. Phys. 103, 2625 (1995)]. The structural and thermodynamic properties calculated from this integral equation show excellent agreement with simulations for both pure fluids and mixtures under the conditions which we have studied. For mixtures, the effect of deviations from the Lorentz-Berthelot (LB) mixing rules for the interaction parameters between unlike species is studied. Positive deviations from the nonadditivity of the molecular cores leads to an entropy driven tendency for the species to separate. This tendency persists even in the presence of a deviation from the LB rule for the energy parameter which enhances the attraction of the unlike species. On the other hand, in the case of negative deviations from nonadditivity, the tendency for association may be either energy or entropy driven, depending on the size ratio.

Communication: Accurate hydration free energies at a wide range of temperatures from 3D-RISM

“…This issue might be addressed using more advanced bridges, of which the method proposed by Duh and Henderson is one such example. 71 This is the subject for future work.…”

Liquid-gas phase behavior of Stockmayer fluid with high dipolar moment

“…RDF g (2) LJ (r), which is needed as an input in (16) and (26), was calculated using OZ equation together with the closure relation suggested by Duh et al [17][18][19]. For the pressure P and chemical potential µ the standard thermodynamical relations…”

“…This function was calculated using solution of the Ornstein-Zernike (OZ) equation supplemented by the closure conditions due to Duh et al [17][18][19].…”

Solvation Thermodynamics of Organic Molecules by the Molecular Integral Equation Theory: Approaching Chemical Accuracy

“…152 Duh, Haymet and Henderson 153,154 used this idea to define a semiempirical (DHH) closure for the OZ equation:…”