Generalized Kohn-Sham system in one-matrix functional theory

Abstract

A system of electrons in a local or nonlocal external potential can be described with one-matrix functional theory (1MFT), which is similar to density-functional theory (DFT) but takes the one-particle reduced density matrix (one-matrix) instead of the density as its basic variable. Within 1MFT, Gilbert derived [Phys. Rev. B 12, 2111 (1975)] effective single-particle equations analogous to the Kohn-Sham (KS) equations in DFT. The self-consistent solution of these 1MFT-KS equations reproduces not only the density of the original electron system but also its one-matrix. While in DFT it is usually possible to reproduce the density using KS orbitals with integer (0 or 1) occupancy, in 1MFT reproducing the one-matrix requires in general fractional occupancies. The variational principle implies that the KS eigenvalues of all fractionally occupied orbitals must collapse at self-consistency to a single level. We show that as a consequence of the degeneracy, the iteration of the KS equations is intrinsically divergent. Fortunately, the level-shifting method, commonly introduced in Hartree-Fock calculations, is always able to force convergence. We introduce an alternative derivation of the 1MFT-KS equations that allows control of the eigenvalue collapse by constraining the occupancies. As an explicit example, we apply the 1MFT-KS scheme to calculate the ground state one-matrix of an exactly solvable two-site Hubbard model.