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 S-1 state of toluene at similar to 460 cm(-1) with a similar to 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 S-1 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. (c) 2006 American Institute of Physics.