A new method for the determination of dynamical features of the molecular dication dissociation processes, following the single photon double ionization, investigated by time-of-flight mass spectrometry technique has been developed. The method is based on an extension of the generalized simulated annealing statistical methodology, previously applied in other fields. Here it is described and applied, as an example, to the case of the dissociation of the CO22+ dication giving CO+ + O+ ion fragments. The results are consistent with previous determination of the metastable lifetime of the dication, but the analysis also provides additional information about the dynamics of the reaction. (C) 2011 Elsevier B. V. All rights reserved.