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Abstract: In the framework of the ‘hot atom’ reaction mechanism we report on the rate of adatom recombination at catalytic surfaces. The modeling deals with a flat surface where hot atoms are identified with the adatoms populating the excited states of the vibrational ladder of the adsorption potential well. The dynamics of the energy transfer between the adlayer and the solid, that is the exchange of vibrational quanta between the adatoms and the solid, has been explicitly taken into account in the master equations together with the adsorption and recombination processes. At steady state the analytical solution of the kinetics is found to be in good agreement with the numerical solutions for a four-levels system. It is shown that the recombination rate at steady state is strongly dependent upon the ratio between the probabilities (per unit time) of quantum dissipation to the solid and of adatom recombination. This ratio is a key quantity of the kinetic model since it rules a continuous transition towards higher rates which is ascribed to a progressive displacement of the vibrational state of the adlayer, from the equilibrium condition. [Copyright &y& Elsevier]