The decay mechanism of photoexcited guanine - A nonadiabatic dynamics study

Ab initio surface hopping dynamics calculations were performed for the biologically relevant tautomer of guanine in gas phase excited into the first π π* state. The results show that the complete population of UV-excited molecules returns to the ground state following an exponential decay within ∼220 fs. This value is in good agreement with the experimentally obtained decay times of 148 and 360 fs. No fraction of the population remains trapped in the excited states. The internal conversion occurs in the state at two related types of conical intersections strongly puckered at the C2 atom. Only a small population of about 5 following an alternative pathway via a n state was found in the dynamics.