Toward a Coherent Theory of Chemisorption

Studies of chemisorption phenomena, the cornerstone of heterogeneous catalysis, have become the central part of contemporary surface science. As a result of the great variety of the available experimental techniques, a backlog of information, some of which conflicts with current theoretical constructs, has accumulated. New models that combine analytical and computational facets have now begun to appear, revealing intrinsic relations among seemingly disparate chemisorption phenomena. Among the major findings are (i) the crucial role of antibonding adsorbate orbitals in bond activation and in the heat of chemisorption, (ii) adsorbate-induced surface polarization leading to a decrease of the metal work function and to an increase of the surface core binding energy, and (iii) important differences between atomic and molecular adsorbate modes of bonding and surface migration.