Partial third-order quasiparticle theory: Comparisons for closed-shell ionization energies and an application to the Borazine photoelectron spectrum

Abstract

Valence ionization energies of a set closed-shell molecules calculated in a partial third-order (P3) quasiparticle approximation of the electron propagator have an average absolute error of 0.19 eV. Diagonal elements of the self-energy matrix include all second-order and some third-order self-energy diagrams. Because of its fifth power dependence on basis set size and its independence from electron repulsion integrals with four virtual indices, this method has considerable potential for large molecules. Formal and computational comparisons with other electron propagator techniques illustrate the advantages of the P3 procedure. Additional applications to benzene and borazine display the efficacy of the P3 propagator in assigning photoelectron spectra. In the borazine spectrum, 2E′ and 2A2′ final states are responsible for an observed feature at 14.76 eV. Another peak at 17.47 eV is assigned to a 2E′ final state.