The yields of multiple Xei+ ions produced by the cascade de-excitations of the L2 to N45 inner shell vacancies are calculated with inclusion of every possible pathway of deexcitation (Auger, Coster-Kronig and radiative) at each branching point of cascade deexcitation trees. Ejections of additional electrons through shake processes are included at each step of de-excitation. Good agreement with the experiment is obtained. Simplified de-excitation schemes suggested earlier by other authors for the initial M-shell vacancies are discussed.

Relative probabilities of monopole shake processes are calculated in the sudden perturbation approximation for atoms with Z between 4 and 71. Most of the calculated data are presented compactly using a simple two-parameter interpolation formula for Z-dependences of shake probabilities per electron.

Final ion charge spectra produced by the cascade de-excitations of 1s- to 5p 3/2-vacancies of the gold atom are calculated by direct construction and analysis of the cascade decay trees. The energies of multivacancy configurations arising in the course of the cascade development, and the partial widths of radiation and radiationless cascade transitions are calculated using the Pauli–Fock approximation. The energies of the cascade transitions are calculated as the differences of total Pauli–Fock energies of initial and final ionic configurations which allowed excluding energy-forbidden radiationless transitions in numerous multivacancy configurations. Partial widths of transitions are expressed in the form that allowed accounting for the effect of electron subshell populations on the transition widths. The partial widths of the transitions between the states of the overlapping initial and final state multiplets are corrected so as to exclude energy-forbidden transitions between the multiplet states. It is demonstrated that accurate accounting for possible forbiddance of transitions between cascade configurations and the exclusion of energy-forbidden term-to-term transitions between the multiplets’ states are crucial in deep-initial-vacancy cascade simulations.