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

Abstract

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 pr..