Ab initio electronic energy calculations are reported for 570 nuclear configurations of LiFH in C s symmetry (three dimensional potential energy surface). The lower five doublet spin-state eigenfunctions (three 2 A′ and two 2 A″) for LiFH have been determined using a multiple reference single and double excitations configuration-interaction (MRDCI) method and an extended triple-zeta-plus-polarization contracted Gaussian basis set. As the Li atom approaches the HF diatomic, it first forms a bent complex (106°) with 28 kJ/mol of stabilization energy before reaching the transition state. The latter, also bent (73°) was located in the exit channel and is predicted to be 24 kJ/mol above the reactants. We argue that laser catalysis of the Li+HF→LiF+H reaction would be possible and irradiation in the 6 000–9 000 cm −1 range is predicted to enhance the reaction.