Microcanonical unimolecular rate theory at surfaces. III. Thermal dissociative chemisorption of methane on Pt(111) and detailed balance.

A local hot spot model of gas-surface reactivity is used to investigate the state-resolved dynamics of methane dissociative chemisorption on Pt(111) under thermal equilibrium conditions. Three Pt surface oscillators, and the molecular vibrations, rotations, and the translational energy directed along the surface normal are treated as active degrees of freedom in the 16-dimensional microcanonical kinetics. Several energy transfer models for coupling a local hot spot to the surrounding substrate are developed and evaluated within the context of a master equation kinetics approach. Bounds on the thermal dissociative sticking coefficient based on limiting energy transfer models are derived. The three-parameter physisorbed complex microcanonical unimolecular rate theory (PC-MURT) is shown to closely approximate the thermal sticking under any realistic energy transfer model. Assuming an apparent threshold energy for CH(4) dissociative chemisorption of E(0)=0.61 eV on clean Pt(111), the PC-MURT is used to predict angle-resolved yield, translational, vibrational, and rotational distributions for the reactive methane flux at thermal equilibrium at 500 K. By detailed balance, these same distributions should be observed for the methane product from methyl radical hydrogenation at 500 K in the zero coverage limit if the methyl radicals are not subject to side reactions. Given that methyl radical hydrogenation can only be experimentally observed when the CH(3) radicals are kinetically stabilized against decomposition by coadsorbed H, the PC-MURT was used to evaluate E(0) in the high coverage limit. A high coverage value of E(0)=2.3 eV adequately reproduced the experimentally observed methane angular and translational energy distributions from thermal hydrogenation of methyl radicals. Although rigorous application of detailed balance arguments to this reactive system cannot be made because thermal decomposition of the methyl radicals competes with hydrogenation, approximate applicability of detailed balance would argue for a strong coverage dependence of E(0) with H coverage--a dependence not seen for methyl radical hydrogenation on Ru(0001), but not yet experimentally explored on Pt(111).