Hydrogen dissociation on metal surfaces - a model system for reactions on surfaces

TL;DR

This paper reviews the theoretical study of hydrogen dissociation on metal surfaces, especially Pd(100), highlighting the role of dynamical effects, electronic structure factors, and quantum influences in surface reactions.

Contribution

It provides insights into the dynamical and electronic factors influencing hydrogen dissociation, including effects of sulfur poisoning and quantum dynamics, based on recent high-dimensional simulations.

Findings

Dynamical concepts like the steering effect are crucial for understanding reactions.

Electronic structure calculations identify factors affecting surface reactivity.

Quantum effects can be assessed by comparing classical and quantum dynamical results.

Abstract

Reactions on surfaces play an important role in many technological applications. Since these processes are often rather complex, one tries to understand single steps of these complicated reactions by investigating simpler system. In particular the hydrogen dissociation on surfaces serves as such a model system. There has been much progress in recent years in the theoretical description of reactions on surfaces by high-dimensional dynamics simulations on potential energy surfaces which are derived from ab initio total energy calculations. In this brief review I will focus on the hydrogen dissociation on the clean and sulfur-covered Pd(100) surface. These calculations established the importance of dynamical concepts like the steering effect. The electronic structure calculations allow furthermore the determination of the factors that determine the reactivity of a particular surface. This will be demonstrated for the poisoning of hydrogen dissociation by sulfur adsorption on the Pd(100) surface. In addition, quantum effects in the dynamics can be assessed by comparing the results of classical with quantum dynamical calculations on the same potential energy surface.