Picosecond time-resolved photoelectron spectroscopy as a means of gaining insight into mechanisms of intramolecular vibrational energy redistribution in excited states

Abstract

We consider the information that can be obtained from time-resolved photoelectron spectroscopy studies of intramolecular vibrational energy redistribution (IVR) in excited states of molecules, focusing on picosecond time-resolved studies of IVR in the intermediate regime. We show that time-resolved measurements may tell us as much about the experimental conditions as they do about the dynamics under examination. We show that carefully controlled picosecond time-resolved photoelectron studies are becoming feasible and that these, combined with robust calculations of Franck–Condon factors, may point the way forward in the quest to understand excited state IVR.