Ambiguity remains in the models explaining the photoinduced dynamics in pentacene thin films as observed in pump-probe experiments. One model advocates exciton fission as governing the evolution of the initially excited species, whereas the other advocates the formation of an excimeric species subsequent to excitation. On the basis of calculations by a combined quantum mechanics and molecular mechanics (QM/MM) method and general considerations regarding the excited states of pentacene we propose an alternative, where the initially excited species instead undergoes internal conversion to a doubly excited exciton. The conjecture is supported by the observed photophysical properties of pentacene from both static as well as time-resolved experiments.