Incorporating the effect of spin–orbit interaction in Auger decay spectra: Theory and examples

N.K. Jayadev, W. Skomorowski, and A.I. Krylov
J. Chem. Phys. , submitted (2025)

A theoretical framework for computing Auger spectra including spin–orbit inter- action is presented. The framework is based on the state-interaction approach using equation-of-motion coupled-cluster wave-functions. The working equations for Auger decay rates are derived within the Feshbach–Fano formalism. The capabilities of the theory are illustrated by calculation of L-edge Auger spectra of H2S and Ar using the Feshbach–Fano (FF) and complex basis function (CBF) approaches. The quality of the Feshbach–Fano results depends critically on the treatment of the free-electron state. In contrast to the K-edge spectra for which both plane wave and Coulomb wave treatments yield reasonable results, the Feshbach–Fano calculations yield accurate results for L-edges only when using Coulomb wave (FF-CW). The FF-CW and CBF calculations of Auger spectra in H2S and Ar agree well with each other and with the available experimental data. The results highlight the importance of spin–orbit interactions for modeling L-edge Auger spectra.

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