LAUSR

ABSTRACT Electron binding energies and Dyson orbitals may be obtained from the poles and residues of the electron propagator. The Dyson quasiparticle equation provides a convenient route to computing this information. Systematic approximations to the latter equation's self-energy, wherein electron correlation and final-state orbital relaxation are described, may be expressed in terms of the elements of the superoperator Hamiltonian matrix. Perturbative methods of electron propagator theory in wide use are based on a reference determinant constructed with canonical, Hartree–Fock orbitals. Generalised matrix elements of the superoperator Hamiltonian that accommodate non-integer occupation numbers associated with general, orthogonal spin orbitals are presented for the first time. Non-Hermitian terms may be systematically eliminated with perturbative corrections to generalised reference density operators. The structure of self-energy approximations that are complete through second, third, fourth or fifth order is presented in terms of superoperator Hamiltonian matrix elements. The present extensions pertain when generalised, zeroth-order density operators expressed in terms of orthonormal spin orbitals are employed. GRAPHICAL ABSTRACT