Open Access

S. M. Tschopp, Hidde D. Vuijk, Abhinav Sharma, J. M. Brader

• The Barker-Henderson perturbation theory is a bedrock of liquid-state physics, providing quantitative predictions for the bulk thermodynamic properties of realistic model systems. However, this successful method has not been exploited for the study of inhomogeneous systems. We develop and implement a first-principles “Barker-Henderson density functional,” thus providing a robust and quantitatively accurate theory for classical fluids in external fields. Numerical results are presented for the hard-core Yukawa model in three dimensions. Our predictions for the density around a fixed test particle and between planar walls are in very good agreement with simulation data. The density profiles for the free liquid vapor interface show the expected oscillatory decay into the bulk liquid as the temperature is reduced toward the triple point, but with an amplitude much smaller than that predicted by the standard mean-field density functional.