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The relativistic corrections beyond the ones from RECPs are still able to double the rate constant of the CH4 + Au+ → HAuCH3 + process at 300 K, while the reverse reaction becomes five times slower. The formation of global products from this intermediate only becomes significant at much higher temperatures (∼1500 K upward). The scalar relativistic contributions decrease the dissociation energy of the initial adduct, AuCH4 +, into the global products by 105.8 kcal mol-1, while the spin-orbit effect provides an extra lowering of 1.8 kcal mo