Ab initio determination of satellite intensities in transition-metal photoemission spectroscopy using a multiconfiguration framework

Following atomic photoionization, the abrupt change in potential can lead to secondary ionization of an outer-shell electron in a phenomenon known as shake-off, a process which gives rise to the asymmetric K alpha profile and satellite lines. Investigation of chemical effects and relativistic quantum mechanics requires a theoretical determination of these satellite intensities; however, existing theoretical predictions are inconsistent with experimental results by up to an order of magnitude. Previously theoretical modeling required up to 12 fitting parameters to account for transition widths, energy corrections, spectator intensities, and spectator broadening. Using a multiconfiguration atomic model to account for electron-electron correlation, we provide here the first ab initio calculations of shake-off probabilities which are in agreement with experimental results (except for copper), an important step toward a complete theoretical profile.