Abstract
Inter- and intra-shell electronic correlations in an atom are manifested in, and can be studied through, the X-ray emission spectra of multielectronic transitions. We have measured the spectra of K hα 1,2 hypersatellites (HS), Kα 3,4 satellites (S), and the 3d electron shake-up satellites (D) accompanying the Kα 1,2 diagram lines, and their evolution from the double-ionization threshold, for selected 4- and 5-row elements of the periodic table. These spectra originate in the [1 s] −1, [2p] −1, and [3d] −1 spectator two-electron transitions [1 s] −2→[1s2p] −1, [1s2p] −1→[2p] −2, and [1s3d] −1→[2p3d] −1 respectively. Photoexcitation by monochromatized synchrotron radiation together with high-resolution crystal spectrometers were employed. Ab initio relativistic multiconfigurational Dirac–Fock (RMCDF) calculations reproduce the spectra very well for all transitions, with the HS spectra showing a strong dependence on QED effects. The excitation thresholds were determined accurately. The threshold-to-saturation energy range of the intensity was found to depend strongly on the principal quantum number n of the spectator hole. For example, for Cu, ranges of 2%, 10%, and 60% of the threshold energy are found for the D, S and HS spectra, respectively. Only the D spectrum's evolution conforms to the Thomas model, indicating a dominant shake up/off process. The S and HS spectra seem to be dominated by the knockout (“two-step-one”) process near threshold. The S spectra show a two-regime behavior. Near threshold both shape and intensity vary with excitation energy, and above that only intensity changes are observed. The lower-than-expected K hα 1/K hα 2 intensity ratio found for Z=23–30 and 39–46 indicates that the angular momenta coupling scheme at the regime intermediate between the LS coupling at low-Z and the jj coupling at high-Z may not be fully accounted for by the prevailing theory.
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