Vibrational non-equilibrium and `hot atomsʹ in the oxidation of carbon monoxide on catalytic surfaces Original Research Article

Non-equilibrium vibrational kinetics, as recently developed for adlayers, is applied to the catalytic oxidation of CO by either molecular or atomic oxygen. This model allows one to fit experimental distribution functions of the product CO2(g) molecules leaving the surface with hyperthermal energies. An LH* mechanism involving non-equilibrium vibrational distribution functions (vdfs) of the relevant adspecies is presented showing the basic consequences of non-equilibrium at the catalytic surface. In this picture `hot atomsʹ are seen as mobile, vibrationally excited adspecies with their vibrational ladders populated according to non-equilibrium Treanor distribution functions.