Probing ultrafast internal conversion of o-xylene via femtosecond time-resolved photoelectron imaging.

The dynamics of excited states in o-xylene molecules has been studied by femtosecond time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. The ultrafast internal conversion from the S(2) state to the vibrationally hot S(1) state on timescale of 60 fs is observed on real time. The secondarily populated high vibronic S(1) state deactivates further to the S(0) state on timescale of 9.85 ps. Interestingly, the lifetime of the low vibronic S(1) state is much longer, extrapolated to ~12.7 ns. The great differences of lifetime of different vibronic S(1) state are due to their different radiationless dynamics.