Benchmarking the Accuracy of Density Functional Theory against the Random Phase Approximation for the Ethane Dehydrogenation Network on Pt(111)
Nicholas A. Szaro, Mubarak Bello, Charles Fricke, Olajide H. Bamidele, Andreas Heyden
Abstract
The Random Phase Approximation (RPA) is conceptually the most accurate Density Functional Approximation method, able to simultaneously predict both adsorbate and surface energies accurately; however, this work questions its superiority over DFT for catalytic application on hydrocarbon systems. This work uses microkinetic modeling to benchmark the accuracy of DFT functionals against that of RPA for the ethane dehydrogenation reaction on Pt(111). Eight different functionals, with and without dispersion corrections, across the GGA, meta-GGA and hybrid classes are evaluated: PBE, PBE-D3, RPBE, RPBE-D3, BEEF-vdW, SCAN, SCAN-rVV10, and HSE06. We show that PBE and RPBE, without dispersion correction, closely model RPA energies for adsorption, transition states, reaction, and activation energies. Next, RPA fails to describe the gas phase energy as unsaturation and chain-length increases in the hydrocarbon. Finally, we show that RPBE has the best accuracy-to-cost ratio, and RPA is likely not superior to RPBE or BEEF-vdW, which also gives a measure of uncertainty.