Limits to scaling relations between adsorption energies?

Linear scaling relations have led to an understanding of trends in catalytic activity and selectivity of many reactions in heterogeneous and electro-catalysis. However, linear scaling between the chemisorption energies of any two small molecule adsorbates is not guaranteed. A prominent example is the lack of scaling between the chemisorption energies of carbon and oxygen on transition metal surfaces. In this work, we show that this lack of scaling originates from different re-normalized adsorbate valence energies of lower-lying oxygen vs higher-lying carbon. We develop a model for chemisorption of small molecule adsorbates within the d-band model by combining a modified form of the Newns-Anderson hybridization energy with an effective orthogonalization term. We develop a general descriptor to a priori determine if two adsorbates are likely to scale with each other.