Linear relationship between activation energies and reaction energies for coverage-dependent dissociation reactions on rhodium surfaces

Abstract

Evidence of a relationship between activation energies and enthalpy changes of various dissociation reactions on transition metals has been reported recently. A reconsideration of density functional theory results for dissociation energies of oxygen and NO on different rhodium surfaces (low-index and stepped) and their dependencies on oxygen precoverage reveal that also here a linear Brønsted–Evans–Polanyi (BEP) relationship exists. The establishment of such a general concept would be of tremendous importance for the development of detailed, elementary-step reaction mechanisms, because the activation energies of reaction steps as well as their coverage dependencies could be estimated based on the adsorption energies calculated by means of DFT.