Ultrafast Photo-Ion Probing of the Relaxation Dynamics in 2-Thiouracil

In this work, we investigate the relaxation processes of 2-thiouracil after UV photoexcitation to the S(2) state through the use of ultrafast, single-colour, pump-probe UV/UV spectroscopy. We place focus on investigating the appearance and subsequent decay signals of ionized fragments. We complement this with VUV-induced dissociative photoionisation studies collected at a synchrotron, allowing us to better understand and assign the ionisation channels involved in the appearance of the fragments. We find that all fragments appear when single photons with energy > 11 eV are used in the VUV experiments and hence appear through 3+ photon-order processes when 266 nm light is used. We also observe three major decays for the fragment ions: a sub-autocorrelation decay (i.e., sub-370 fs), a secondary ultrafast decay on the order of 300–400 fs, and a long decay on the order of 220 to 400 ps (all fragment dependent). These decays agree well with the previously established S(2) → S(1) → Triplet → Ground decay process. Results from the VUV study also suggest that some of the fragments may be created by dynamics occurring in the excited cationic state.