Despite its importance, it is still not known by which mechanism Li-doped MgO catalyzes the oxidative coupling of methane to ethane. Nevertheless, it is commonly assumed that the mechanism goes through catalytic H abstraction from methane via a Li+O– surface defect. In this paper we use first-principles density functional theory calculations to show that the reaction is significantly more exothermic when the Li+O– defect is situated on a step edge instead of on the flat surface. We find that the reaction on the step is exothermic by 0.25 eV, whereas it is endothermic by 0.3 eV on the flat surface. The presence of the Li dopant in the step edge is crucial for the exothermicity of the reaction. These findings suggest that surface steps which include lithium defects could be responsible for the catalytic behavior of Li/MgO. Following the binding of hydrogen to the Li+O– defect on the step edge the methyl radical can either depart to the gas phase or bind to an adjacent step-edge oxygen atom, increasing the exothermicity of the overall process to 0.8 eV. Activation energies of 0.2 eV for the first pathway and 0.5–0.8 eV for the second were calculated.

The dissociation dynamics of oxygen on silver surfaces is studied theoretically. The method is based on a quantum-mechanical time-dependent non-adiabatic picture. A universal functional form for the potential energy surfaces is employed. The diabatic potentials describing the sequence of events leading to dissociation begin from the physisorption potential crossing over to a charged molecular chemisorption potential and crossing over again to the dissociated atomic-surface potential. Within such a potential surface topology, two different surfaces leading to dissociation are studied: the empirical potential of Spruit and the ab-initio potential of Nakatsuji. It is found that the system is captured by the molecular chemisorption well for a considerable length of time, long enough for thermalization. Thus the calculation is split into two parts: the calculation of “direct” dissociation probability and the calculation of nonadiabatic dissociative tunneling rate from the thermalized chemisorbed molecular state. For the direct probabilities, the Fourier method with the Chebychev polynomial expansion of the evolution operator is used to solve the time-dependent Schrödinger equation. For the tunneling rate calculation, a similar expansion of Green's operator is used. The output of the direct-reaction calculation is the dissociation probability as a function of the initial energy content, while the tunneling calculation yields the dissociation rate. The dependence of the direct dissociation probability on the initial kinetic energy is found to be non-monotonic. A strong isotope effect has been found, favoring the dissociation of the light species.