The valence orbital momentum distributions and binding energy spectra of silane by electron momentum spectroscopy: Quantitative comparisons using Hartree-Fock limit and correlated wavefunctions

Abstract

The binding energies and momentum distributions of the two valence orbitals of SiH 4 have been measured by electron momentum spectroscopy. The measured binding energy spectrum is compared with ADC(3) and ADC(4) many-body Green function calculations. The momentum distributions are compared on a quantitative basis with SCF wavefunctions near the Hartree-Fock limit and also with full ion-neutral overlap calculations carried out using correlated wavefunctions by the method of configuration interaction. Quite good agreement with theory is found at the Hartree-Fock limit and inclusion of electron correlation has minimal effect on the calculated momentum distributions. A study of the angular dependence of the satellite structure in the inner valence region shows that these processes arise predominantly from final state correlations associated with the production of the 3a 1 −1 hole state.