Classical density functional theory of orientational order at interfaces: Application to water

Jaqaman K., Tuncay K., Ortoleva P.

JOURNAL OF CHEMICAL PHYSICS, vol.120, no.2, pp.926-938, 2004 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 120 Issue: 2
  • Publication Date: 2004
  • Doi Number: 10.1063/1.1630012
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.926-938
  • Middle East Technical University Affiliated: No


A classical density functional formalism has been developed to predict the position-orientation number density of structured fluids. It is applied to the liquid-vapor interface of pure water, where it consists of a classical term, a gradient correction, and an anisotropic term that yields order through density gradients. The model is calibrated to predict that water molecules have their dipole moments almost parallel to a planar interface, while the molecular plane is parallel to it on the liquid side and perpendicular to it on the vapor side. For a planar interface, the surface tension obtained is twice its experimental value, while the surface potential is in qualitative agreement with that calculated by others. The model is also used to predict the orientation of water molecules near the surface of droplets, as well as the dependence of equilibrium vapor pressure around them on their size. (C) 2004 American Institute of Physics.