The ground and very low-lying excited states of LiGa and NaGa have been studied using high level ab initio techniques. At the QCISD(T)/6-311 + G(2df) level of theory, the 1 Σ + state was found to be the most stable for both molecules. The equilibrium bond lengths and dissociation energies were found to be: R(Li-Ga) = 2.865 and D 0 (LiGa) = 22.3 kcal/mol and R(Na-Ga) = 3.174 and D 0 (NaGa) = 17.1 kcal/mol. Trends within the ground electronic states of LiB, NaB, LiAl, NaAl, LiGa and NaGa are discussed and predictions for related AlkM (alk = Li-Cs and M = B-Tl) species are made.