Determination of kinetic properties in unimolecular dissociation of complex systems from graph-theory based analysis of an ensemble of reactive trajectories

International audience ; In this paper we report how graph-theory can be used to analyze an ensemble of independent molecular trajectories which can react during the simulation time-length and obtain structural and kinetic information. The method is totally general and here is applied to the prototypical case of gas phase fragmentation of protonated cyclo-di-glycine. The methodology allows to analyze the whole set of trajectories in an automatic computer-based way without the need of visual inspection, but getting all the needed information. In particular, we not only determine the appearance of different products and intermediates, but we can characterize the corresponding kinetics. The use of colored-graph and canonical labeling allows the correct characterization of the chemical species involved. In the present case, the simulations consist of an ensemble of unimolecular fragmentation trajectories at constant energy, such that from the rate constants at different energies the threshold energy can also be obtained for both global and specific pathways. This approach allows the characterization of ion-molecule complexes, likely through a roaming mechanism, by properly taking into account the elusive nature of such species. Finally, it is possible to obtain directly the theoretical mass spectrum of the fragmenting species if the reacting system is an ion, as in the specific example.