Abstract. The fundamental measure density functional theory for hard spheres is generalized to binary mixtures of arbitrary positive and moderate negative non-additivity between unlike components. In bulk the theory predicts fluid–fluid phase separation into phases with different chemical compositions. The location of the accompanying critical point agrees well with previous results from simulations over a broad range of non-additivities and both for symmetric and highly asymmetric size ratios. Results for partial pair correlation functions show good agreement with simulation data.

Print publication: Issue 30 (4 August 2004)
Received 18 June 2004
Published 16 July 2004