Isothermal kinetic measurements on elementary steps between species adsorbed on solid surfaces have highlighted significant deviations from conventional kinetic theories. In particular, it has been found that neighboring adsorbates modify the energetics of surface reaction in ways not explained by macroscopic kinetic models. The free energy barriers associated with transition state theory can be expanded to include coverage-dependent terms, but that does not account for local effects due to surface islanding. Changes in surface concentrations also lead to changes in adsorption geometries, and even to different adsorbate-surface bonding. Future Monte Carlo simulations and other theoretical approaches to describe surface kinetics need to include these factors.
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Francisco Zaera (2002) studied this question.
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