Triple ionization of HCl via states with a 2p core hole

The triple ionization of HCl by double Auger decay and related processes has been studied using a multiparticle coincidence technique combined with synchrotron radiation. Four contributing processes are identified; direct double Auger, two indirect double Auger decay pathways, and single Auger decay from core-valence doubly ionized intermediate states. One indirect Auger process involves autoionization from superexcited states of Cl⁺. Double Auger decay from HCl⁺ (2p^-1, ²P_J), which makes up 11% ± 2% of total Auger decay, is estimated to be 40% direct, 15% indirect via atomic Cl^+* and 45% indirect via molecular intermediate doubly ionized states. The vertical triple ionization energy of HCl is determined as 73.8 ± 0.5 eV. Molecular field effects are found to affect the direct double Auger process as well as normal single Auger decay. A comparison between spectra of the HCl and DCl isotopomers indicates that electronic decay is faster in all the processes than molecular dissociation.