Interpretation of the silver L x-ray spectrum

A new analysis of the Ag L-series x-ray spectrum has been performed, based on relaxed-orbital relativistic transition-energy calculations. Satellite energies were computed in intermediate coupling. It is found that satellites arising from LN double-hole states generally fall within the natural width of the parent diagram lines. Contrary to previous assumption, the observed high-energy satellites are due to LM double-hole states produced by L₁-L₃M4,5 Coster-Kronig transitions and by shakeoff. The observed peak structure in the satellite spectrum is due to multiplet splitting of the initial and final double-hole states. Theoretical L₁-L₃M4,5 transition rates based on the new Coster-Kronig energies are closer to experiment than previous results, but still are too large by a factor of {~}2, indicating an as yet undetected flaw in the theory.