The momentum distributions and binding energies of the valence orbitals of phosphine by electron momentum spectroscopy: Quantitative comparisons using near Hartree-Fock limit and correlated wavefunctions

Abstract

The binding energies and electron momentum distributions for the three valence orbitals of PH 3 have been measured by high resolution electron momentum spectroscopy. The measured binding energy spectrum, which shows extensive structure in the inner valence region, is compared with CI and many-body Green function calculations. The momentum distributions are compared on a quantitative basis with a range of SCF wavefunctions up to near the Hartree-Fock limit in quality and also with full ion-neutral overlap calculations carried out using correlated wavefunctions by the method of conf'iguration interaction. Inclusion of electron correlation is found to have minimal effect on the calculated momentum distributions.