Energies of the hollow molecules CH42+ and NH32+ with double vacancies in the 1s shells have been measured using an efficient coincidence technique combined with synchrotron radiation. The energies of these states have been determined accurately by high level electronic structure calculations and can be well understood on the basis of a simple theoretical model. Their major decay pathway, successive Auger emissions, leads first to a new form of triply charged ion with a core hole and two valence vacancies; experimental evidence for such a state is presented with its theoretical interpretation. Preedge 2-hole-1-particle (2h-1p) states at energies below the double core-hole states are located in the same experiments and their decay pathways are also identified.
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