Spectra of the triply charged ion CS₂³⁺ and selectivity in molecular Auger effects

Spectra of triply charged carbon disulphide have been obtained by measuring, in coincidence, all three electrons ejected in its formation by photoionization. Measurements of the CS₂³⁺ ion in coincidence with the three electrons identify the energy range where stable trications are formed. A sharp peak in this energy range is identified as the ²Π ground state at 53.1±0.1 eV, which is the lowest electronic state according to ab initio molecular orbital calculations. Triple ionization by the double Auger effect is provisionally divided, on the basis of the pattern of energy sharing between the two Auger electrons into contributions from direct and cascade Auger processes. The spectra from the direct double Auger effect via S 2p, S 2s, and C 1s hole states contain several resolved features and show selectivity based on the initial charge localization and on the identity of the initial state. Triple ionization spectra from single Auger decay of S 2p -based core-valence states CS₂²⁺ show retention of the valence holes in this Auger process. Related ion-electron coincidence measurements give the triple ionization yields and the breakdown patterns in triple photoionization at selected photon energies from 90 eV to above the inner shell edges.