Best-of-both-worlds computational approaches to difficult-to-model dissociation reactions on metal surfaces

Abstract

The accurate modeling of dissociative chemisorption of molecules on metal surfaces presents an exciting scientific challenge to theorists, and is practically relevant to modeling heterogeneously catalyzed reactive processes in computational catalysis. The first important scientific challenge in the field is that accurate barriers for dissociative chemisorption are not yet available from first principles methods. For systems that are not prone to charge transfer (for which the difference between the work function of the surface and the electron affinity of the molecule is less than 7 eV) this problem can be circumvented: chemically accurate barrier heights can be extracted with a semi-empirical version of density functional theory (DFT). However, a second important challenge is posed by systems that are prone to (full or partial) electron transfer from the surface to the molecule. For these systems the Born-Oppenheimer approximation breaks down, and currently no method of established accuracy exists for modeling the resulting effect of non-adiabatic energy dissipation on the dissociative chemisorption reaction. Because two problems exist for this class of reactions, a semi-empirical approach to computing barrier heights, which would demand that computed and experimental dissociative chemisorption probabilities match, is unlikely to work. This Perspective presents a vision on how these two problems may be solved. We suggest an approach in which parameterized density functionals are used as in the previous semi-empirical approach to DFT, but in which the parameters are based on calculations with first principles electronic structure methods. We also suggest that the diffusion Monte-Carlo (DMC) and the random phase approximation (RPA) probably are the best two first principles electronic structure methods to pursue in the framework of the approach that we call first-principles based DFT (FPB-DFT) – providing DMC and the RPA with a steppingstone towards benchmarking and future applications in computational catalysis. Probably the FPB density functional is best based on screened hybrid exchange in combination with non-local van der Waals correlation.There is a second paragraph we cannot at this stage include, but we feel it should be there, Please see the uploaded paper.