Ab initio treatment of molecular Coster-Kronig decay using complex-scaled equation-of-motion coupled-cluster theory.

Vacancies in the L 1 shell of atoms and molecules can decay non-radiatively via Coster-Kronig decay whereby the vacancy is filled by an electron from the L 2,3 shell while a second electron is emitted into the ionization continuum. This process is akin to Auger decay, but in contrast to Auger electrons, Coster-Kronig electrons have rather low kinetic energies of less than 50 eV. In the present work, we extend recently introduced methods for the construction of molecular Auger spectra that are based on complex-scaled equation-of-motion coupled-cluster theory to Coster-Kronig decay. We compute ionization energies as well as total and partial decay widths for the 2s -1 states of argon and hydrogen sulfide and construct the L 1 L 2,3 M Coster-Kronig and L 1 MM Auger spectra of these species. Whereas our final spectra are in good agreement with the available experimental and theoretical data, substantial disagreements are found for various branching ratios suggesting that spin-orbit coupling makes a major impact on Coster-Kronig decay already in the third period of the periodic table.