Observation of a simple vibrational wavepacket in a polyatomic molecule via time-resolved photoelectron velocity-map imaging: a prototype for time-resolved IVR studies.

We have prepared a coherent superposition of the two components of a Fermi resonance in the S1 state of toluene at approximately 460 cm(-1) with a approximately 1 ps laser pulse and monitored time-resolved photoelectron velocity-map images. The photoelectron intensities oscillate with time in a manner that depends on their kinetic energy, even though full vibrational resolution in the cation is not achieved. Analysis of the time-dependent photoelectron spectra enables information on the composition of the S1 wavepacket to be deduced. Such an experiment, in which a whole set of partially dispersed cation vibrational states are detected simultaneously, suggests an efficient method of studying intramolecular vibrational energy redistribution processes in excited states.