Towards chemically accurate simulation of molecule–surface reactions

Abstract

This perspective addresses four challenges facing theorists whose aim is to make quantitatively accurate predictions for reactions of molecules on metal surfaces, and suggests ways of meeting these challenges, focusing on dissociative chemisorption reactions of H₂, N₂, and CH₄. Addressing these challenges is ultimately of practical importance to a more accurate description of overall heterogeneously catalysed reactions, which play a role in the production of more than 90% of man-made chemicals. One challenge is to describe the interaction of a molecule with a metal surface with chemical accuracy, i.e., with errors in reaction barrier heights less than 1 kcal mol⁻¹. In this framework, the potential of a new implementation of specific reaction parameter density functional theory (SRP-DFT) will be discussed, with emphasis on applications to reaction of H₂ with metal surfaces. Two additional challenges are to come up with improved descriptions of the effects of phonons and electron–hole pairs on reaction of molecules like N₂ on metal surfaces. Phonons can be tackled using sudden approximations in quantum dynamics, and through Ab Initio Molecular Dynamics (AIMD) calculations using classical dynamics. To additionally achieve an accurate description of the effect of electron–hole pair excitation on dissociative chemisorption within a classical dynamics framework, it may be possible to combine AIMD with electronic friction. The fourth challenge we will consider is how to achieve an accurate quantum mechanical description of the dissociative chemisorption of a polyatomic molecule, like methane, on a metal surface. A method of potential interest is the Multi-Configuration Time-Dependent Hartree (MCTDH) method.