Jump to main content
Jump to site search

Issue 30, 2012
Previous Article Next Article

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

Author affiliations

Abstract

The ultrafast excited state relaxation of ammonia is investigated by resonantly exciting specific vibrational modes of the electronically excited NH3 (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 NH3 (Ã) state which manifests itself as coupling of the umbrella (ν2) and symmetric N–H stretch (ν1) 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 (Ã)/NH3 ([X with combining tilde]) conical intersection and has shown that upon non-adiabatic dissociation into NH2 ([X with combining tilde]) + H, the NH2 ([X with combining tilde]) fragment is predominantly generated with significant fractions of internal vibrational energy.

Graphical abstract: Observation of ultrafast NH3 (Ã) state relaxation dynamics using a combination of time-resolved photoelectron spectroscopy and photoproduct detection

Back to tab navigation

Supplementary files

Article information


Submitted
18 Jan 2012
Accepted
12 Mar 2012
First published
15 Mar 2012

Phys. Chem. Chem. Phys., 2012,14, 10401-10409
Article type
Paper

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

N. L. Evans, H. Yu, G. M. Roberts, V. G. Stavros and S. Ullrich, Phys. Chem. Chem. Phys., 2012, 14, 10401
DOI: 10.1039/C2CP40178A

Social activity

Search articles by author

Spotlight

Advertisements