Towards a spectroscopically accurate set of potentials for heavy hydride laser cooling candidates: effective core potential calculations of BaH

BaH (and its isotopomers) is an attractive molecular candidate for laser cooling to ultracold temperatures and a potential precursor for the production of ultracold gases of hydrogen and deuterium. The theoretical challenge is to simulate the laser cooling cycle as reliably as possible and this paper addresses the generation of a highly accurate ab initio $^{2}\Sigma^+$ potential for such studies. The performance of various basis sets within the multi-reference configuration-interaction (MRCI) approximation with the Davidson correction (MRCI+Q) is tested and taken to the complete basis set limit. It is shown that the calculated molecular constants using a 46 electron Effective Core-Potential (ECP), the augmented polarized core-valence quintuplet basis set (aug-pCV5Z-PP) but only including three active electrons in the MRCI calculation are in close agreement with the available experimental values. The predicted dissociation energy D$_e$ for the X$^2\Sigma^+$ state (extrapolated to the complete basis set (CBS) limit) is 16895.12 cm$^{-1}$ (2.094 eV), which agrees within 0.1$\%$ of a revised experimental value of $<$16910.6 cm$^{-1}$, while the calculated r$_e$ is within 0.03 pm of the experimental result.
Comment: 14 pages, 9 figures: final accepted version