The Ultrafast Vibronic Dynamics of Ammonia's D̃ State.

Using vacuum-ultraviolet time-resolved velocity map imaging of photoelectrons, we study ultrafast coupled electronic and nuclear dynamics in low-lying Rydberg states of ammonia. Vibrationally-resolved internal vibrational relaxation (IVR) is observed in a progression of the e' bending modes. This vibrational progression is only observed in the D̃ state, and is lost upon ultrafast internal conversion to the C̃ and B̃ electronic states. Due to the ultrashort time scale of the internal conversion (ca. 64 fs), and the vibronic resolution, the non-adiabatic coupling vectors are identified and verified with ab initio calculations. The time-scale of this IVR process is highly surprising and significant because IVR is usually treated as an incoherent process that proceeds statistically, according to a "Fermi's Golden Rule"-like model, where the process scales with the available degrees of freedom. Here, we show that it can be highly non-statistical, restricted to only a very small subset of vibrational motions.