Unraveling the Metastability of C(n)(2+) (n = 2–4) Clusters

[Image: see text] Pure carbon clusters have received considerable attention for a long time. However, fundamental questions, such as what the smallest stable carbon cluster dication is, remain unclear. We investigated the stability and fragmentation behavior of C(n)(2+) (n = 2–4) dications using state-of-the-art atom probe tomography. These small doubly charged carbon cluster ions were produced by laser-pulsed field evaporation from a tungsten carbide field emitter. Correlation analysis of the fragments detected in coincidence reveals that they only decay to C(n–1)(+) + C(+). During C(2)(2+) → C(+) + C(+), significant kinetic energy release (∼5.75–7.8 eV) is evidenced. Through advanced experimental data processing combined with ab initio calculations and simulations, we show that the field-evaporated diatomic (12)C(2)(2+) dications are either in weakly bound (3)Π(u) and (3)Σ(g)(–) states, quickly dissociating under the intense electric field, or in a deeply bound electronic (5)Σ(u)(–) state with lifetimes >180 ps.