A theoretical study of Li2H. I. Basis set and computational survey of excited states and possible reaction paths

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Abstract
SCF potential curves for C2v (Li2+H) and C∞v (LiH+Li) symmetries have been calculated for the 26 lowest lying states of Li2H. The curves are estimated to be ≲0.1 eV above the Hartree–Fock–Roothaan limit. Correlated MCSCF/CI curves were computed for the lowest states of 2A1, 2B2, and 2Σ symmetries. All low‐lying states of the complex Li2H involve substantial charge transfer. The most stable of these, 2A1, lies ∼20 kcal/mole below the ground state LiH+Li asymptote. The first excited state of the complex, 2B2, is but weakly bound relative to the same asymptote. Electron‐jump geometries and vertical spectra were computed for all of these low‐lying states. Possible low‐energy paths for the reaction Li2+H→LiH+Li were determined, and all involve charge‐transfer intermediates.