Fig. 7: Free energy profile of the catalytic cycle at 750 K.
Entropy-corrected free energies of the intermediates (i) and transition states (TS) in the catalytic decomposition of exo-C10H16 on the global minimum structure of TiAl2B6 cluster (structure 1 in Fig. 5) at 750 K. The geometries of the TS’s are represented in Supplementary Fig. 15. The catalytic steps include - a C-H and C-C activations of exo-C10H16 and b desorption of the products from the TiAl2B6 cluster. The dotted connections are uphill on the enthalpic potential energy surfaces and show no TS, while some of them get strongly stabilized by entropy and appear significantly downhill (such as i6 → i7) in the free energy surface; the associated entropic barriers are not computed as they are not expected to alter the reaction kinetics.
