First-principles derivation of density functional formalism for quenched-annealed systems

Abstract

We derive from first principles (without resorting to the replica trick) a density-functional theory for fluids in quenched disordered matrices (QA-DFT). We show that the disorder-averaged free energy of the fluid is a functional of the average density profile of the fluid as well as the pair correlation of the fluid and matrix particles. For practical reasons it is preferable to use another functional: the disorder-averaged free energy plus the fluid-matrix interaction energy, which, for fixed fluid-matrix interaction potential, is a functional only of the average density profile of the fluid. When the matrix is created as a quenched configuration of another fluid, the functional can be regarded as depending on the density profile of the matrix fluid as well. In this situation, the replica Ornstein-Zernike equations which do not contain the blocking parts of the correlations can be obtained as functional identities in this formalism, provided the second derivative of this functional is interpreted as the connected part of the direct correlation function. The blocking correlations are totally absent from QA-DFT, but nevertheless the thermodynamics can be entirely obtained from the functional. We apply the formalism to obtain the exact functional for an ideal fluid in an arbitrary matrix, and discuss possible approximations for nonideal fluids.