Ensemble Ground State of a Many-Electron System with Fractional Electron Number and Spin: Piecewise-Linearity and Flat-Plane Condition Generalized.

Abstract

Description of many-electron systems with a fractional electron number (Ntot) and fractional spin (Mtot) is of great importance in physical chemistry, solid-state physics, and materials science. In this Letter, we provide an exact description of the zero-temperature ensemble ground state of a general, finite, many-electron system and characterize the dependence of the energy and the spin-densities on both Ntot and Mtot, when the total spin is at its equilibrium value. We generalize the piecewise-linearity principle and the flat-plane condition and determine which pure states contribute to the ground-state ensemble. We find a new derivative discontinuity, which manifests for spin variation at a constant Ntot, as a jump in the Kohn-Sham potential. We identify a previously unknown degeneracy of the ground state, such that the total energy and density are unique, but the spin-densities are not. Our findings serve as a basis for development of advanced approximations in density functional theory and other many-electron methods.