Electronic structure, reactivity, and spectroscopy of dihydrides of group-IB metals

International audienceAtomic pseudopotentials and highly correlated wave functions, including spin-orbit interactions, have been used to evaluate the electronic structure, stability, and spectroscopy of triatomic molecule MH2, with a metal M belonging to group IB (Cu, Ag, and Au). CuH2 and AuH2 have been recently observed by IR spectroscopy in solid hydrogen and bending anharmonic wave numbers have been assigned to these two systems. The AgH2 molecule has not been detected nor experimentally characterized, despite several theoretical works arguing on its stability. Our results confirm that the MH2 radicals have a metastable bent ground state separated from the dissociation into [M+H-2] ground state by barriers which have been evaluated to 1.43, 0.78, and 0.80 eV, for Cu, Ag, and Au compounds, respectively. These barriers are calculated smaller than in previous determinations but still large enough to stabilize the MH2 systems. Spectroscopic data are calculated for these radicals

Electronic structure and spectroscopy of monohalides of metals of group I-B

International audienceThe potential energy curves of the low lying electronic states of nine molecular compounds MX (M = Cu, Ag, An; X = F, Cl, Br) have been calculated by ab initio multi-reference configuration interaction (MRCI) and coupled-cluster (CC) methods using scalar-relativistic energy-consistent pseudopotentials. The electronic structures of these compounds have been analysed and compared. New spin-orbit (SO) pseudopotentials for Cu, Ag and Au have been optimised and applied for determining the SO splitting of the correlated states. In this way, accurate spectroscopic data have been derived that lead to new assignments and predictions for electronic states unobserved so far