Functional theory of extended Coulomb systems

A consistent formulation is presented for a functional theory of extended quantum many-particle systems with long-range Coulomb interactions, which extends the density-functional theory of Hohenberg and Kohn to encompass the theory of dielectrics formulated in terms of electric fields and polarization. We show that a complete description of insulators in the thermodynamic limit requires a functional of density and macroscopic polarization; nevertheless, for any insulator the state with zero macroscopic electric field can be considered a reference state that is a functional of the density alone. Dielectric phenomena involve the behavior of the material in the presence of macroscopic electric fields that induce changes of the macroscopic polarization from its equilibrium value in the reference state. In the thermodynamic limit there is strictly no ground state and constraints must be placed upon the electronic wave functions in order to have a well-defined energy functional; within these constrained subspaces the Hohenberg-Kohn theorems can be generalized in terms of the density and the change in the macroscopic polarization. The essential role of the polarization is shown by an explicit example of two potentials that lead to the same periodic density in a crystal, but different macroscopic electric fields and polarization. In the Kohn-Sham approach both the kinetic and the exchange-correlation energy are shown to depend upon the changes in polarization; this leads to generalized Kohn-Sham equations with a nonlocal operator. The effect can be traced to the polarization of the average exchange-correlation hole itself in the presence of macroscopic fields, which is essential for an exact description of static dielectric phenomena.