The dissociative chemisorption dynamics of N2 on catalytic metal surfaces: A quantum-mechanical tunneling mechanism

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Abstract
A tunneling mechanism is suggested for explaining the dissociative chemisorption of nitrogen molecules on metal surfaces. The time‐dependent Schrödinger equation was numerically solved for the transition dynamics from the N2–metal to the N–metal potential‐energy surfaces for two degrees of freedom. The dynamics was found to be sensitive to the topology at the crossing region between the two nonadiabatic potential‐energy surfaces (PES). The resulting rapid increase of the dissociation probability (S0) with incident kinetic energy, its saturation at high energies and vibrational enhancement are in good agreement with recent experiments. A substantial isotope effect is predicted by the calculations. Recombinative desorption experiments of 14N2 and 15N2 from Re(0001) are in excellent agreement with the tunneling model.