Pseudopotential and electron propagator methods for the calculation of the photoelectron spectra of anionic silicon clusters: Predictions on Si10−

Abstract

Photoelectron spectra of anionic clusters of silicon require reliable theoretical calculations for their assignment and interpretation. Electron propagator calculations in the outer valence Green's-function approximation with two well-characterized, all-electron basis sets on vertical electron detachment energies (VEDEs) of anions are compared to similar calculations that employ Stuttgart pseudopotentials. Tests on Si(n) (-) clusters with n=3-7 exhibit an encouraging agreement between the all-electron and pseudopotentials results and between electron propagator predictions and experiments and values obtained from coupled-cluster calculations. To illustrate the capabilities of the new approach based on a Si pseudopotential and electron propagator methods, VEDE calculations on Si(10) (-) are presented.