Best-of-Both-Worlds Predictive Approach to Dissociative Chemisorption on Metals.

Predictive capability, accuracy, and affordability are essential features of a theory that is capable of describing dissociative chemisorption on a metal surface. This type of reaction is important for heterogeneous catalysis. Here we present an approach in which we use diffusion Monte Carlo (DMC) to pin the minimum barrier height and construct a density functional that reproduces this value.

Constructing Mixed Density Functionals for Describing Dissociative Chemisorption on Metal Surfaces: Basic Principles.

The production of a majority of chemicals involves heterogeneous catalysis at some stage, and the rates of many heterogeneously catalyzed processes are governed by transition states for dissociative chemisorption on metals. Accurate values of barrier heights for dissociative chemisorption on metals are therefore important to benchmarking electronic structure theory in general and density functionals in particular. Such accurate barriers can be obtained using the semiempirical specific reaction parameter (SRP) approach to density functional theory.

Simulating Highly Activated Sticking of H on Al(110): Quantum versus Quasi-Classical Dynamics.

We evaluate the importance of quantum effects on the sticking of H on Al(110) for conditions that are close to those of molecular beam experiments that have been done on this system. Calculations with the quasi-classical trajectory (QCT) method and with quantum dynamics (QD) are performed using a model in which only motion in the six molecular degrees of freedom is allowed. The potential energy surface used has a minimum barrier height close to the value recently obtained with the quantum Monte Carlo method.

SBH17: Benchmark Database of Barrier Heights for Dissociative Chemisorption on Transition Metal Surfaces.

Accurate barriers for rate controlling elementary reactions on metal surfaces are key to understanding, controlling, and predicting the rate of heterogeneously catalyzed processes. While barrier heights for gas phase reactions have been extensively benchmarked, dissociative chemisorption barriers for the reactions of molecules on metal surfaces have received much less attention. The first database called SBH10 and containing 10 entries was recently constructed based on the specific reaction parameter approach to density functional theory (SRP-DFT) and experimental results.