Reaction dynamics on surfaces in the harmonic approximation

Abstract

We suggest a method for calculating the rates of reactions involving adsorbates on the surfaces of a semi-infinite solid. The method makes use of multidimensional quantum transition-state theory to obtain an expression for the rate. Using the harmonic approximation, one can take into account all vibrational degrees of freedom of the solid. The final expression for the rate is expressed in terms of a few matrix elements of the Green function for the perfect solid (one in which there are no adsorbates). As there exist efficient methods for evaluation of the required matrix elements, it is possible to apply the procedure to various processes like desorption, diffusion and recombination on the surfaces.