Theory of copper Kα and Kβ diagram lines, satellite spectra, and ab initio determination of single and double shake probabilities

•First calculation of dominant satellite spectra according to shake probabilities.•Iterative formal convergence to 10 times better than past work, to 0.03 eV.•First calculation of subshell satellite shake and double-shake probabilities.•Remarkable agreement to 0.032 eV with most recent accurate experiment to date. High-accuracy MCDHF Cu Kα and Cu Kβ diagram spectra and major satellites are presented. Spectral eigenvalues reach a theoretical expansion convergence of 0.03 eV or 0.00025%, with gauge and amplitude convergence to 0.7% for Cu Kα diagram spectra. Dominant theoretical spectral eigenvalues are shown to be within 0.032 eV of experimental data. Ab initio shake-off contributions are presented in terms of total probability from each subshell and as separated single and double shake probabilities. Discrepancies between theory and experiment in copper X-ray spectra arise from profile asymmetries, relativistic terms and shake spectra not yet accounted for. These results and this improved agreement provide key fundamental parameters for processes towards XFEL evolution and resolving key discrepancies between theory and experiment.