Picosecond pump–probe photoelectron spectroscopy as a probe of intramolecular dynamics in S1 para-fluorotoluene

Picosecond photoelectron spectroscopy is used to monitor the intramolecular dynamics in S1 parafluorotoluene prepared with ∼1200 cm−1 of internal energy from a jet cooled sample. The spectra evolve dramatically over a 100 ps timescale supporting results from chemical timing experiments. This suggests that initial temperature has little effect on the energy redistribution rate.