The UBI-QEP method: Basic formalism and applications to chemisorption phenomena on transition metal surfaces. Chemisorption energetics

摘要

The paper reviews the state of the art in the unity bond index-quadratic exponential potential (UBI-QEP) method. Assumptions made in the framework of the method, as well as their validity and generality, are discussed. The method is based only on well-defined observable energetic and structural parameters. UBI-QEP formulas for calculating reaction energetics (the binding energies of atomic and molecular adsorbates, the reaction enthalpies, and the intrinsic activation barriers) at different surface coverages are discussed. The UBI-QEP formalism is best suited for calculations of the adsorption of atoms and diatomic molecules but also allows one to consider polyatomic molecules in the quasi-diatomic approximation. A new formalism is discussed for determining the binding energies of various polyatomic molecules without resorting to hypothetical (and largely ambiguous) bond energy partitioning schemes. Instead, this new formalism considers the total bond energy of gas-phase species, which is an observable value. This formalism is the recent advance in the method. Various examples of calculating the energetics of atomic and molecular adsorption are presented. In most cases, the agreement of calculated and experimental values is good. The UBI-QEP method makes it possible to consider uniformly various processes on metal surfaces: adsorption, dissociation, diffusion, recombination, disproportionation, and desorption. Examples of complicated UBI-QEP calculations of molecular adsorption are presented.