Exploring Ultrafast H-Atom Elimination versus Photofragmentation Pathways in Pyrazole Following 200 nm Excitation

The role of ultraviolet photoresistance in many biomolecules (e.g., DNA bases and amino acids) has been extensively researched in recent years. This behavior has largely been attributed to the participation of dissociative (1)pi sigma* states localized along X-H (X = N, O) bonds, which facilitate an efficient means for rapid nonradiative relaxation back to the electronic ground state via conical intersections or ultrafast H-atom elimination. One such species known to exhibit this characteristic photochemistry is the UV chromophore imidazole, a subunit in the biomolecules adenine and histidine. However, the (1)pi sigma* driven photochemistry of its structural isomer pyrazole has received much less attention, both experimentally and theoretically. Here, we probe the ultrafast excited state dynamics occurring in pyrazole following photoexcitation at 200 nm (6.2 eV) using two experimental methodologies. The first uses time-resolved velocity map ion imaging to investigate the ultrafast H-atom elimination dynamics following direct excitation to the lowest energy (1)pi sigma* state (1(1)A '' <- X(1)A'). These results yield a bimodal distribution of eliminated H-atoms, situated at low and high kinetic energies, the latter of which we attribute to (1)pi sigma* mediated N-H fission. The time constants extracted for the low and high energy features are similar to 120 and <50 fs, respectively. We also investigate the role of ring deformation relaxation pathways from the first optically bright (1)pi pi* state (2(1)A' <- X(1)A'), by performing time-resolved ion yield measurements. These results are modeled using a (1)pi pi* -> ring deformation -> photofragmentation mechanism (a model based on comparison with theoretical calculations on the structural isomer imidazole) and all photofragments possess appearance time constants of <160 fs. A comparison between time-resolved velocity map ion imaging and time-resolved ion yield measurements suggest that (1)pi sigma* driven N-H fission gives rise to the dominant kinetic photoproducts, re-enforcing the important role (1)pi sigma* states have in the excited state dynamics of biological chromophores and related aromatic heterocycles.