Photoelectron spectroscopy of S1 toluene: I. Photoionization propensities of selected vibrational levels in S1 toluene.

Laser photoelectron spectra have been obtained following the preparation of eight vibrational states in S₁ toluene. For four of the vibrational states (up to ∼550 cm^-1 excess energy) excitation and ionization with nanosecond laser pulses give rise to photoelectron spectra with well-resolved vibrational peaks. For the other states (>750 cm^-1 excess energy) the photoelectron spectra show a loss of structure when nanosecond pulses are used, as a result of intramolecular dynamics [see Whiteside et al., J. Chem. Phys. 123, 204317 (2005), following paper]. A number of vibrational peaks in the photoelectron spectra are assigned, and we find that the common series of ion vibrational peaks observed following the ionization of p-fluorotoluene in various S₁ vibrational states is not reproduced in toluene. [ABSTRACT FROM AUTHOR]