Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu

Abstract

With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces serves as a prototype for comparing experiment and theory. Previously measured pre-exponential factors for CO₂ formation from formate on metal surfaces, including Cu(110), are substantially higher than expected from the often used value of k_BT/h, or ∼6 × 10¹² s⁻¹, suggesting that the entropy of the transition state is higher than that of the adsorbed formate. Herein, the rate constant parameters for formate decomposition on Au(110) and Cu(110) are addressed quantitatively by both experiment and theory and compared. A pre-exponential factor of 2.3 × 10¹⁴ s⁻¹ was obtained experimentally on Au(110). DFT calculations revealed the most stable configuration of formate on both surfaces to be bidentate and the transition states to be less rigidly bound to the surface compared to the reactant state, resulting in a higher entropy of activation and a pre-exponential factor exceeding k_BT/h. Though reasonable agreement is obtained between experiment and theory for the pre-exponential factors, the activation energies determined experimentally remain consistently higher than those computed by DFT using the GGA–PBE functional. This difference was largely erased when the metaGGA–SCAN functional was applied. This study provides insight into the underlying factors that result in the relatively high pre-exponential factors for unimolecular decomposition on metal surfaces generally, highlights the importance of mobility for the transition state, and offers vital information related to the direct use of DFT to predict rate constants for elementary reaction steps on metal surfaces.