Femtosecond real-time probing of reactions MMXVII: The predissociation of sodium iodide in the A 0+ state

Abstract

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.