Improving Molecule-Metal Surface Reaction Networks Using the Meta-Generalized Gradient Approximation: CO2 Hydrogenation

17 November 2023, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Density functional theory (DFT) is widely used to gain insight in molecule-metal surface reaction networks, which is important for a better understanding of catalysis. However, it is well known that generalized gradient approximation (GGA) density functionals (DF), most often used for the study of reaction networks, struggle to correctly describe both gas-phase molecules and metal surfaces. Also, GGA DFs typically underestimate reaction barriers due to an underestimation of the self-interaction energy. Screened hybrid GGA DFs have been shown to reduce this problem, but are currently intractable for wide usage. In this work we use a more affordable meta-generalized gradient approximation (mGGA) DF in combination with a non-local correlation DF for the first time to study a catalytically important surface reaction network, namely CO2 hydrogenation on Cu. We show that the mGGA DF used, namely rMS-RPBEl-rVV10, outperforms typical GGA DFs by providing similar or better predictions for metals, molecules, as well as molecule-metal surface adsorption and activation energies. Hence, it is a better choice for constructing molecule-metal surface reaction networks.


reaction network
CO2 hydrogenation
Cu catalyst

Supplementary materials

Supporting Information
Computational setup (S.1); Convergence of computational parameters for HCOOH adsorption energy (S.2); Formulas for the calculation of gibbs free energy (S.3); adsorption energy and adsorption sites for all intermediates on Cu(111) and Cu(211) calculated with rMS-RPBEl-rVV10 (S.4); List of (adsorbed) species and corresponding energies, entropies, zero-point energy and thermal corrections calculated with rMS-RPBEl-rVV10, BEEF-vdW and RPBE-D3 (S.5); Detailed analysis of formate, carboxyl, and CO2 dissociation pathway on Cu(111) and Cu(211) (S.6)


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