Quantum computation solves a half-century-old enigma: Elusive vibrational states of magnesium dimer found

The high-lying vibrational states of the magnesium dimer (Mg(2)), which has been recognized as an important system in studies of ultracold and collisional phenomena, have eluded experimental characterization for half a century. Until now, only the first 14 vibrational states of Mg(2) have been experimentally resolved, although it has been suggested that the ground-state potential may support five additional levels. Here, we present highly accurate ab initio potential energy curves based on state-of-the-art coupled-cluster and full configuration interaction computations for the ground and excited electronic states involved in the experimental investigations of Mg(2). Our ground-state potential unambiguously confirms the existence of 19 vibrational levels, with ~1 cm(−1) root mean square deviation between the calculated rovibrational term values and the available experimental and experimentally derived data. Our computations reproduce the latest laser-induced fluorescence spectrum and provide guidance for the experimental detection of the previously unresolved vibrational levels.