Doubly charged dimers and trimers of heavy noble gases

Many doubly charged heteronuclear dimers are metastable or even thermodynamically stable with respect to charge separation. Homonuclear dicationic dimers, however, are more difficult to form. He₂²⁺ was the first noble gas dimer predicted to be metastable and, decades later, observed. Ne₂²⁺ is the only other dicationic noble gas dimer that has been detected so far. Here, we present a novel approach to form fragile dicationic species, by post-ionization of singly charged ions that are embedded in helium nanodroplets (HNDs). Bare ions are then extracted by colliding the HNDs with helium gas. We detect homonuclear doubly charged dimers and trimers of krypton and xenon, but not argon. Our multi-reference ab initio calculations confirm the stability of Kr₂²⁺, Kr₃²⁺, Xe₂²⁺, Xe₃²⁺, and Ar₂²⁺, but put the stability of Ar₃²⁺ towards dissociation to Ar⁺ + Ar₂⁺ into question.