Exploring the Time Scales of H-Atom Elimination from Photoexcited Indole

Recent spectroscopic measurements have shown that following excitation of indole molecules above the (1)pi pi*-(1)pi sigma* conical intersection, photoinduced N-H bond cleavage results in a range of H-atom kinetic energy release. H-atoms with large amounts of kinetic energy were attributed to direct dissociation whereas those with low kinetic energy were attributed to indirect pathways such as statistical unimolecular decay. With use of a combination of femtosecond pump-probe spectroscopy and velocity map ion-imaging techniques, both energy and time-resolved photoinduced H-atom elimination at 200 nm has been measured. The results show that H-atoms with both high and low kinetic energies are generated on an ultrafast time scale, <200 fs, suggesting that on the time frame of our measurements (<200 ps) there appears to be a direct route to H-atom formation yielding H-atoms with low kinetic energies.