[en] Highlights: • Femtosecond transition-state spectroscopy of sodium iodide was revisited. • Modern lasers and pulse shaping techniques were used to probe NaI predissociation. • Accurate ab initio potentials of NaI including spin-orbit coupling were obtained. • Time dependent wave packet dynamics of NaI in the A 0⁺ state were simulated. We revisit the femtosecond transition-state spectroscopy of sodium iodide taking advantage of modern lasers and pulse-shaping to better map the low-lying electronic states, some forming predissociative wells through curve crossings. We also carry out high-level ab initio multi-reference configuration interaction calculations including spin-orbit coupling terms and using large correlation-consistent basis sets to arrive at accurate ground- and excited-state potential energy curves of NaI. Density matrix calculations employing vibrational wave functions determined from the ab initio X 0⁺ and A 0⁺ potentials are used to simulate time dependent wave packet dynamics of NaI pumped to the A 0⁺ state.