Classical density functional theory for associating fluids in orienting external fields

Abstract

We develop a classical density functional theory (DFT) for two-site associating fluids in spatially homogeneous external fields which exhibit orientational inhomogeneities. The Helmholtz free-energy functional is obtained using Wertheim's thermodynamic perturbation theory and the orientational distribution function is obtained using DFT in the canonical ensemble. It is shown that an orientating field significantly enhances association by ordering the molecules, thereby reducing the entropic penalty of association. It is also shown that association enhances the orientational order for fixed field strength.