The interaction of NOxon Ni(111) surface investigated with quantum-chemical calculations.

We applied periodic density-functional theory to investigate the interaction of NOxon Ni(111) surface for small and large coverages. For a small coverage, adsorbed species, such as NO, N2O and NO2, tend to dissociate to form atomic N and atomic O on the surface, but a large barrier, 2.34 eV, hinders the recombination of adsorbed N to form N2. At a large coverage, the recombination of N and NO to form N2O is favorable; this species might either desorb or break the N–O bond to form N2. Our calculated results agree satisfactorily with experimental observations. The formation of N2viapaths that vary with coverage is analyzed and discussed. [ABSTRACT FROM AUTHOR]