Referenced in: none

Automatically associated channels: TRP

Title: Observation of ultrafast NH(3) (Ã) state relaxation dynamics using a combination of time-resolved photoelectron spectroscopy and photoproduct detection.

Authors: Nicholas L Evans, Hui Yu, Gareth M Roberts, Vasilios G Stavros, Susanne Ullrich

Journal, date & volume: , 2012 Apr 12 , ,

PubMed link: http://www.ncbi.nlm.nih.gov/pubmed/22499282

Abstract
The ultrafast excited state relaxation of ammonia is investigated by resonantly exciting specific vibrational modes of the electronically excited NH(3) (Ã) 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 σ* mediated relaxation of the NH(3) (Ã) state which manifests itself as coupling of the umbrella (ν(2)) and symmetric N-H stretch (ν(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 NH(2) 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 NH(3) (Ã)/NH(3) (X̃) conical intersection and has shown that upon non-adiabatic dissociation into NH(2) (X̃) + H, the NH(2) (X[combining tilde]) fragment is predominantly generated with significant fractions of internal vibrational energy.