Vapour-liquid equilibria for Stockmayer fluids with rigid and polarizable dipoles

An equation of state contribution for polar components: Polarizable dipoles

“…The renormalized fluid is one with the effective dipole moment (rather than the value in vacuo) and with no polarizability, and the problem is thus rephrased in terms of two‐body and three‐body correlations. The theory was extended to mixtures and comprehensively described by Venkatasubramanian et al,20 Joslin et al,21 and Gray et al22 If we restrict our considerations to bulk properties (excluding the dielectric behavior of a fluid), the RPT, despite its elegance, was next applied only a decade later, when Kriebel and Winkelmann23–25 developed an equation of state for polarizable spherical and polarizable two‐center Lennard‐Jones molecules with embedded dipole moment. They used a simplified implementation of RPT and compared their model to their own molecular simulation data.…”

Orthogonal polynomial approach to fluids with internal degrees of freedom: The case of polar, polarizable molecules

“…Table I lists the results for MD cases reported by Pollock, Alder, and Patey 23 for a state near the triple point density, 3 ϭ0.8 and k B T/ϭ1. 35. The three closures give generally similar results.…”

“…[23][24][25] These calculations follow the integral equation procedures described above, using three specific closures: optimized reference-hypernetted chain ͑RHNC͒, 26-28 hypernetted chain ͑HNC͒, 12 and single superchain ͑SSC͒, 29 also known as linearized HNC ͑LHNC͒. In the numerical work, integrals over r are evaluated using the trapezoidal rule on a grid of N r ϭ1024 points with an interval ⌬r/ϭ0.02.…”

“…No converged solution of the RHNC or HNC equation was found for the next state reported by Pollock et al, ␣ 0 / 3 ϭ0.050 for the same 0 . Although the last state for which a solution was obtained lies in the neighborhood of the two-phase region, 35 MSA, these complex solutions can be understood as the origin of optical absorption 36 when a frequency dependent polarizability model is used. In the context of our nonlinear approach this is however less clear.…”

Bulk and Surface Properties of Dipolar Fluids

“…Other authors have focused on the isotropic-ferromagnetic spinodal which corresponds to a divergence of the dielectric constant, whose position can be estimated using correlation functions from different integral equation theories [13,14]. Finally, we mention perturbation theory as an alternative approach to determine successfully liquid-vapor coexistence of Stockmayer fluids with rigid or polarizable dipoles [15][16][17][18].…”