title: Orbital Energies for Seniority-Zero Wave Functions.
abstract: A new single-pair operator for seniority-zero wave functions is introduced closely related to the single-particle Fock operator from conventional Hartree-Fock theory. This allows one to ascribe orbital energies in the context of model Hamiltonians, for which no single-particle operators exist. Several applications demonstrate the usefulness of these orbital energies. In analogy to Koopmans' theorem, atomic double ionization potentials are successfully predicted. A computationally efficient second-order perturbation scheme for seniority-zero wave functions scaling quadratically with system size is defined and applied to the dissociation of nitrogen and to strongly correlated two-dimensional Heisenberg lattices. An extension of the method for full seniority is presented leading to an intruder-free single reference perturbation theory with improved asymptotic convergence.
authors.affiliation: Institute of Physical Chemistry, Karlsruhe Institute of Technology , D-76131 Karlsruhe, Germany.
authors.forename: Peter A
authors.initials: PA
authors.lastname: Limacher