The density functional theory of classical fluids revisited

Abstract

We reconsider the density functional theory of nonuniform classical fluids from the point of view of convex analysis. From the observation that the logarithm of the grand-partition function $\log Ξ[ϕ]$ is a convex functional of the external potential $ϕ$ it is shown that the Kohn-Sham free energy ${\cal A}[ρ]$ is a convex functional of the density $ρ$. $\log Ξ[ϕ]$ and ${\cal A}[ρ]$ constitute a pair of Legendre transforms and each of these functionals can therefore be obtained as the solution of a variational principle. The convexity ensures the unicity of the solution in both cases. The variational principle which gives $\log Ξ[ϕ]$ as the maximum of a functional of $ρ$ is precisely that considered in the density functional theory while the dual principle, which gives ${\cal A}[ρ]$ as the maximum of a functional of $ϕ$ seems to be a new result.