Comparison of rotationally inelastic rate constants for Li2A1Σu+(vi=5,ji=30) + Ne measured using pulsed and cw lasers

► Pulsed and cw laser excitation of a molecule lead to equivalent rate constants. ► Differences in the velocity distributions lead the pulsed values to be slightly (13%) higher. ► This difference is confirmed by quasiclassical trajectories run on an ab initio surface.