The UBI-QEP method: A practical theoretical approach to understanding chemistry on transition metal surfaces

Abstract

In this review we examine the presently available theoretical techniques for determining metal surface reaction energetics. The unity bond index-quadratic exponential potential (UBI-QEP) method, which provides heats of adsorption and reaction activation barriers with a typical accuracy of 1–3 kcal/mol, emerges as the method with the widest applicability for complex and practically important reaction systems. We discuss in detail the theoretical foundations of the analytic UBI-QEP method which employs the most general two-body interaction potentials. The potential variable, named a bond index, is a general exponential function of the two-center bond distance. The bond indices of interacting bonds are assumed to be conserved at unity (up to the dissociation point), and we cite state-of-the-art ab initio calculations to support this assumption. The UBI-QEP method allows one to calculate the reaction energetics in a straightforward variational way. We summarize the analytic formulas for adsorbate binding energies in various coordination modes and for intrinsic and diffusion activation barriers. We also describe a computer program which makes UBI-QEP calculations fully automated. The normalized bond index-molecular dinamics, (NBI-MD) simulation technique, which is an adaptation of the UBI-QEP reactive potential functions to molecular dynamics, is described. Detailed summaries of applications are given which include the Fischer-Tropsch synthesis, oxygen assisted X-H bond cleavage, hydrogen peroxide, methanol and ammonia syntheses, decomposition and reduction of NO, and SO x chemistry.