Energy partition dynamics in CO oxidation on transition metal surfaces

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Measurements of both vibrational and rotational energies of product CO_2 in CO oxidation on palladium surfaces have been successfully performed as a function of the desorption angle by means of infrared chemiluminescence. The remarkable angle dependences of both energies indicate facile energy partitioning in repulsive desorption and provide new dimensions in the study of surface reaction dynamics as well as additional insights into the product formation site.On Pd(110) (1×1), with increases in polar angle, both energies decreased in the [001] direction but remained constant in [110]. On Pd(110) (1×2), both energies increased in [001] but decreased in [110]. On Pd(111), the rotational energy greatly increased, but the vibrational energy decreased. Such angular dependence of internal energy of products has never been observed in any surface reactions. From these results, it is possible to predict structures of transition states.