Observation of ultrafast NH3 ((A)over-tilde) state relaxation dynamics using a combination of time-resolved photoelectron spectroscopy and photoproduct detection

The ultrafast excited state relaxation of ammonia is investigated by resonantly exciting specific vibrational modes of the electronically excited NH3 ((A) over tilde) state using three complementary femtosecond (fs) pump-probe techniques: time-resolved photoelectron, ion-yield and photofragment translational spectroscopy. Ammonia can be seen as a prototypical system for studying non-adiabatic dynamics and therefore offers a benchmark species for demonstrating the advantages of combining the aforementioned techniques to probe excited state dynamics, whilst simultaneously illuminating new aspects of ammonia's photochemistry. Time-resolved photoelectron spectroscopy (TRPES) provides direct spectroscopic evidence of sigma* mediated relaxation of the NH3 ((A) over tilde) state which manifests itself as coupling of the umbrella (nu(2)) and symmetric N-H stretch (nu(1)) modes in the photoelectron spectra. Time-resolved ion yield (TRIY) and time-resolved photofragment translation spectroscopy (TRPTS) grant a measure of the dissociation dynamics through analysis of the H and NH2 photodissociation co-fragments. Initial vibrational level dependent TRIY measurements reveal photoproduct formation times of between 190 and 230 fs. Measurement of H-atom photoproduct kinetic energies enables investigation into the competition between adiabatic and non-adiabatic dissociation channels at the NH3 ((A) over tilde)/NH3 ((X) over tilde) conical intersection and has shown that upon non-adiabatic dissociation into NH2 ((X) over tilde + H, the NH2 ((X) over tilde) fragment is predominantly generated with significant fractions of internal vibrational energy.