Automated reaction mechanism generation

Contemporary chemical kinetics and the theory of reaction mechanisms are characterized not only by increased complexity of the mechanisms (hypotheses of mechanisms) but also by the considerable number of hypotheses (the possible mechanisms describing each reaction). Cases are known where the mechanism of formation of a certain product in a complicated multiroute mechanism incorporates completely different sequences of elementary steps and intermediates" even in the case of reactions that have one linearly independent stoichiometric equation The greater mechanistic complexity and high number of hypotheses raise the issue of the formalization and automation of the procedure adopted for the generation of hypotheses. 

In recent years rate estimation techniques gained substantial interest because they are needed for automated mechanism generation algorithms and new estimation approaches and improved rate rules are still currently developed. The example discussed above is only intended to provide a first glance of how such estimations can be made with rather little knowledge of the reaction details. 

Another important feature of DigiSim is automated curve fitting. An experimental voltammogiam can be imported and fitted to the theory generated for the chosen mechanism and geometry. Figure 15.11 shows the fit between the experimental and theoretical CVs obtained for the square scheme, which involves two ET steps coupled with two homogeneous reactions. 

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