Langmuir, Vol.14, No.2, 396-406, 1998
Estimation of the surface tension of polar fluids - Long-range contributions
The theoretical prediction of the surface tension of polar fluids is considered with the focus on the long-range contributions arising due to orientational correlations among the dipoles. A set of three different methods are applied to a simple model of a polar fluid : (i) A very simple analysis is presented based on an effective dipole-dipole potential and the use of the generalized van der Waals (GvdW) density functional theory which has proven to be quite accurate for Lennard-Jones fluids. The effective dipole-dipole potential retains, in a low-order approximation, the Lennard-Jones form of the full potential but adds temperature dependence to the potential parameters. (ii) Molecular dynamics (MD) simulations provide a far more accurate account of the short-range interaction in the polar fluid but suffer from numerical difficulties associated with the need for a cutoff on the range of the interaction to which the surface tension is particularly sensitive. (iii) For this reason we introduce a hybrid MD/GvdW theory wherein the long-range contribution to the surface tension is estimated by the corresponding term in the GvdW result. Applications to the single-component fluids composed of HCl or HBr are presented. The interaction potential is taken to be of either Stockmayer form or a closely related form where the dipole moment is created by two point charges. The results show that the GvdW estimate agrees reasonably with experiment, and MD simulation and MD/GvdW calculation improves the xonvergence of the MD estimate by inclusion of both direct long-range interaction and indirect effects due to changes in the bulk phases.
Keywords:GENERALIZED VANDERWAALS THEORY;LIQUID-VAPOR INTERFACE;MOLECULAR-DYNAMICS SIMULATION;DENSITY-FUNCTIONAL THEORY;DIPOLAR FLUIDS;THERMODYNAMIC PROPERTIES;COMPUTER-SIMULATION;WATER;COEXISTENCE;ADSORPTION