Dynamic Features of Transition States for β‐Scission Reactions of Alkenes over Acid Zeolites Revealed by AIMD Simulations

Zeolite‐catalyzed alkene cracking is key to optimize the size of hydrocarbons. The nature and stability of intermediates and transition states (TS) are, however, still debated. We combine transition path sampling and blue moon ensemble density functional theory simulations to unravel the behavior of C7 alkenes in CHA zeolite. Free energy profiles are determined, linking π‐complexes, alkoxides and carbenium ions, for B1 (secondary to tertiary) and B2 (tertiary to secondary) β‐scissions. B1 is found to be easier than B2. The TS for B1 occurs at the breaking of the C−C bond, while for B2 it is the proton transfer from propenium to the zeolite. We highlight the dynamic behaviors of the various intermediates along both pathways, which reduce activation energies with respect to those previously evaluated by static approaches. We finally revisit the ranking of isomerization and cracking rate constants, which are crucial for future kinetic studies. Ab initio molecular dynamics shows that alkene cracking mechanisms and kinetics, as catalyzed by protonic zeolites, differ strongly as a function of the reactant and product structures. This is due to the dynamic nature of the transition structures, which either correspond to β‐scissions or to proton transfers to the zeolite. Secondary carbenium ions are not stable reaction intermediates, whereas tertiary cations and π‐complexes are.