The Ensemble Ghost Interaction in Fractional-Occupation Hartree-Fock: Occupation Covariance, Pair Rank, and Prescribed Ensembles of Determinants

Abstract

Fractional Occupation Number unrestricted Hartree-Fock (FON-UHF) evaluates the UHF functional on a density matrix with non-integer occupations. Sector-Averaged UHF (SA-UHF) averages the energies of a prescribed ensemble of determinants, possibly from different particle-number sectors, on common orbitals. The two differ by the ensemble ghost interaction G. We show that, for two determinants, the numbers of spin-orbitals gained and lost between them classify G before any calculation. G vanishes on every orbital set at pair rank one, has a fixed sign at pair rank two and whenever two or more spin-orbitals are only gained or only lost, and otherwise has an orbital-dependent sign. For larger ensembles, G vanishes on every orbital set when all pair covariances of the occupations vanish, and in the complete-basis limit only then. The same pairs add a covariance term to the orbital gradient and give the error of the chemical potential estimated from the ensemble Fock matrix. We implemented both methods in the eT program. The calculations give G = 0.24 Hartree at half transfer for the hexaamminecobalt(III/II) couple, 78-84% of the FON-UHF penalty for a fraction shared between the degenerate frontier orbitals of benzene, and the limit 1/(4R) for a hole shared between two stacked ethylene molecules.