Both periodic and YARP-cluster results predict that type I reactions are exothermic. Therefore, cycle (2) may not dominate the reaction network. Indeed, previous experimental results of Ga single sites show a strong selectivity to olefin oligomerization at 250 °C and 1 atm, forming short linear oligomers. ) However, the cracking activation energy becomes lower as the temperature increases due to a favorable entropic effect (more degrees of freedom) on the reverse type I step versus the formation of longer Ga-alkyl carbon chain, thus narrowing the energy difference between Ga-2-butyl (species 7 ) and the cracking TS. Entropy can also shift the equilibrium since cycle (2) produces a higher number of gas molecules than cycle (1), suggesting that cycle (2) becomes more favorable at higher temperatures. Finally, the high barrier of the reverse type I step provides a basis for the competition between type I and III reactions starting from the Ga-2-butyl species. In particular, the formation of 1-butane (species 6 -3 c ) can be competitive with cracking reactions (species 7 -8 ). Subsequently, acetylene formation can occur via facile type II reactions (species 4 c -5 c ,1.68 eV). Therefore, our pathway analysis suggests that type III reactions are kinetically less favorable, but nevertheless represent side-reaction channels that becomes accessible as they compete with the reverse of type I step. With the formation of alkynes, other side reactions, such as aromatization and coking, may occur as subsequent thermodynamic products.