Understanding the influence of solvents on the Pt-catalyzed hydrodeoxygenation of guaiacol

Benchmarking the Accuracy of Density Functional Theory against the Random Phase Approximation for the Ethane Dehydrogenation Network on Pt(111)

“…Therefore, as a general trend and especially for the dispersion corrected methods, apparent errors for reaction energies and activation barriers are smaller than the referenced adsorption and transition state energies. This has beneficial effects as reaction energies and activation barriers are directly used in a microkinetic model and adsorption/desorption steps (where we do not have the same level of error cancellation) are usually few in number and can otherwise be corrected independently. , Lastly, given the availability of experimental adsorption and/or desorption energies of alkanes on Pt(111), we benchmarked the zero-point corrected adsorption reaction energies of methane and ethane on Pt(111) computed through the different DFT functionals and ACFDT-RPA to experimental values in Table S3 of the Supporting Information. We found that ACFDT-RPA, HSE06 and the GGA dispersion uncorrected functionals (PBE and RPBE) all demonstrate a significant underestimation (underbinding) of the experimental values, while Grimme D3 dispersion corrected GGA functional (PBE-D3 and RPBE-D3) show significant overestimation (overbinding).…”