Concepts in Theoretical Heterogeneous Catalytic Reactivity

Introduction A. General The heart of many commercial catalytic processes involves chemistry on transition metal particles and surfaces. The success in designing active surface ensembles, promoters, and selective poisons is inevitably tied to our knowledge of the fundamental principles which control transition metal surface chemistry. One extreme would be the rigorous description and energetic predictions for each elementary reaction step of an entire catalytic cycle from first-principle theoretical methods. While desirable, this has to date been an unattainable goal due to the limitations in both raw computer (CPU) requirements and the accuracy of the available computational methods. Recent advances in both quantum-chemical methods and computational resources, however, are driving this goal closer to reality. Theoretical treatments of adsorbate-surface interactions have rapidly advanced to the stage where detailed understandings of the governing structural and electronic features are readily available. In...