Full-Dimensional Ab Initio Potential Energy Surface and Vibrational Energy Levels of Li2H

We built a full-dimensional analytical potential energy surface of the ground electronic state of Li2H from ca. 20,000 ab initio multi-reference configuration interaction calculations, including core–valence correlation effects. The surface is flexible enough to accurately describe the three dissociation channels: Li (2s 2S) + LiH (1Σ+), Li2 (1Σg+) + H (1s 2S) and 2Li (2s 2S) + H (1s 2S). Using a local fit of this surface, we calculated pure (J = 0) vibrational states of Li2H up to the barrier to linearity (ca. 3400 cm−1 above the global minimum) using a vibrational self-consistent field/virtual state configuration interaction method. We found 18 vibrational states below this barrier, with a maximum of 6 quanta in the bending mode, which indicates that Li2H could be spectroscopically observable. Moreover, we show that some of these vibrational states are highly correlated already ca. 1000 cm−1 below the height of the barrier. We hope these calculations can help the assignment of experimental spectra. In addition, the first low-lying excited states of each B1, B2 and A2 symmetry of Li2H were characterized.